Process for producing a fluorine-containing compound by liquid phase fluorination

ABSTRACT

The invention provides a process for producing a fluorine-containing compound from an inexpensive material. 
     Namely, Compound I such as R A CH 2 OH is reacted with Compound II such as XCOR B  to form Compound III such as R A CH 2 OCOR B , followed by fluorination in a liquid phase to form Compound IV such as R AF CF 2 OCOR BF , which is converted to Compound V such as R AF COF and/or Compound VI such as R BF COF. R A  is an alkyl group or the like, R B  is a perhalogenoalkyl group or the like, R AF  and R BF  are fluorinated R A  and R B , and X is halogen.

This application is a Continuation of International Appl. No.PCT/JP00/01765 filed on Mar. 23, 2000.

TECHNICAL FIELD

The present invention relates to a process for producing afluorine-containing compound such as an industrially useful acidfluoride compound. Further, the present invention provides a novelcompound which is useful as a precursor for a fluorine resin material.

BACKGROUND ART

Heretofore, as a method for fluorinating all of C—H portions in a C—Hcontaining compound to C—F, a method of employing cobalt trifluoride, amethod of direct fluorination with fluorine gas, or a method of carryingout a fluorination reaction in an electrolytic cell using electrolyzedhydrogen fluoride as a fluorine source (hereinafter referred to aselectrochemical fluorination) has been known. The method of employingcobalt trifluoride is one wherein the reaction is carried out at a hightemperature by a gas-solid reaction, whereby isomerization or bondbreakage takes place, and there is a problem that various types ofby-products will form. In the case where a direct fluorination method iscarried out with fluorine gas, a gas phase method or a liquid phasemethod has been known. However, the gas phase reaction has a problemthat during the fluorination reaction, dissociation of C—C single bondstakes place, and various types of by-products will form. In recentyears, a liquid phase method has been reported.

On the other hand, a method for fluorination in a liquid phase byreacting fluorine gas to a non-fluorine containing compound, has alsobeen reported (U.S. Pat. No. 5,093,432). Further, a method for obtainingan acid fluoride compound by thermal decomposition of a perfluorinatedester compound having a carbon number of at least 16, has also beenknown, and it is disclosed that the compound can be obtained by directfluorination of a hydrocarbon ester compound having a correspondingstructure in a liquid phase with fluorine gas (J. Am. Chem. Soc.,120,7117(1998)).

The method of employing cobalt trifluoride or electrochemicalfluorination has had a problem such that an isomerization reaction takesplace or a problem such that breakage of the main chain, a re-unionreaction, etc., may occur, and has had a drawback that the desiredcompound can not be obtained in good purity. In a case where afluorination reaction is carried out in a liquid phase with fluorinegas, it is common to employ a solvent capable of dissolving fluorinegas, as the solvent for the reaction. However, a hydrocarbon compound asa starting material in a conventional method, usually has a lowsolubility in a solvent to be used for the fluorination reaction, andaccordingly, the reaction is carried out in a very low concentration,whereby there has been a problem that the production efficiency is pooror a problem that the reaction will have to be carried out in asuspension which is disadvantageous to the reaction. Further, if it isattempted to fluorinate a hydrocarbon compound of a low molecular weightin a liquid phase, a problem has been observed such that the reactionyield tends to be remarkably low.

On the other hand, a fluorine-containing monomer such as aperfluoro(alkylvinyl ether) is useful as a starting material monomer fora fluorinated resin having heat resistance and chemical resistance.Heretofore, the perfluoro(alkylvinyl ether) has been industriallyproduced by a dimerization reaction of a perfluorinated epoxide or byreacting a perfluoroalkanoyl fluoride with a perfluorinated epoxide inthe presence of an alkali Or metal fluoride to form aperfluoro(2-alkoxyalkanoyl)fluoride, followed by thermal decomposition.However, such a method has had a problem that control of the reaction ofthe dimerization reaction is difficult, and the price of the startingmaterial is high and economically disadvantageous.

DISCLOSURE OF THE INVENTION

In the present invention, as a result of various studies on the causefor problems of the conventional methods, firstly, it has been foundthat the cause for the low yield in the fluorination reaction in aliquid phase with fluorine gas, is attributable to the fact that if theboiling point of the starting material is low, the starting materialwill react in a gas phase so that a decomposition reaction takes place.Then, it has been found that the decomposition reaction can be preventedby using an inexpensively available C—H containing compound as thestarting material, converting it to a compound of a specific structurewhich has a high molecular weight so that a gas phase reaction hardlytakes place and which is soluble in a solvent for the fluorinationreaction, followed by fluorination in a liquid phase. Further, it hasbeen found that the desired fluorine-containing compound can be producedby dissociation of a bonded group after fluorination (for example,dissociation by means of a thermal decomposition reaction or adecomposition reaction carried out in the presence of a nucleophile oran electrophile). Further, an industrial continuous process by recyclingthe formed compound, has been found.

Namely, the present invention provides a process for producing afluorine-containing compound, characterized by reacting the followingcompound (I) with the following compound (II) to form the followingcompound (III), fluorinating the compound (III) in a liquid phase toform the following compound (IV) and then converting the compound (IV)to the following compound (V) and/or the following compound (VI):

R^(A)—E¹ (I)

 R^(B)—E² (II)

R^(A)—E—R^(B) (III)

R^(AF)—E^(F)R^(BF) (IV)

R^(AF)—E^(F1) (V)

R^(BF)—E^(F2) (VI)

wherein

R^(A), R^(B): each independently is a monovalent saturated hydrocarbongroup, a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, ahalogeno(hetero atom-containing monovalent saturated hydrocarbon) group,or a monovalent organic group (R^(H)) which can be converted to R^(HF)by a liquid-phase fluorination reaction,

R^(HF): a group having at least one hydrogen atom in a group selectedfrom a monovalent saturated hydrocarbon group, a partially halogenomonovalent saturated hydrocarbon group, a hetero atom-containingmonovalent saturated hydrocarbon group, and a partially halogeno(heteroatom-containing monovalent hydrocarbon) group, substituted by a fluorineatom;

R^(AF), R^(BF): R^(AF) is a group corresponding to R^(A), and R^(BF) isa group corresponding to R^(B); and in a case where each of R^(A) andR^(B) is a monovalent saturated hydrocarbon group, a halogeno momovalentsaturated hydrocarbon group, a hetero atom-containing monovalentsaturated hydrocarbon group, or a halogeno(hetero atom-containingsaturated hydrocarbon) group, R^(AF) and R^(BF) are the same groups asR^(A) and R^(B), respectively, or groups having at least one fluorineatom present in the groups of R^(A) and R^(B) substituted by a fluorineatom, and in a case where R^(A) and R^(B) are monovalent organic groups(R^(H)), R^(AF) and R^(BF) are R^(HF), respectively;

E¹, E²: reactive groups which are mutually reactive to form a bivalentconnecting group (E);

E: a bivalent connecting group formed by the reaction of E¹ and E^(2;)

E^(F): the same group as E, or a group having E fluorinated, providedthat at least one of R^(AF), R^(BF) and E^(F), is not the same group asthe corresponding R^(A), R^(B) and E, respectively;

E^(F1), E^(F2): each independently is a group formed by dissociation ofE^(F).

Further, the present invention provides the following novel compounds,provided that in this specification, Cy is a cyclohexyl group, Ph is aphenyl group, and Cy^(F) is a perfluoro(cyclohexyl) group;

CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH (OCH₂CH₂CH₃)CH₃,

CF₃CF₂COOCH₂CH₂CHClCH₂Cl,

CF₂ClCFClCF₂COOCH₂CH₂CHClCH₂Cl,

CF₂ClCF₂CFClCOOCH₂CH₂CHClCH₂Cl,

CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂CH₂CHClCH₂Cl) CH₃,

CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH (OCH₂Cy) CH₃,

CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂Ph)CH₃,

CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(O(CH₂)₉CH₃)CH₃,

CF₃(CF₃CF₂CF₂O)CFCOO(CH₂)₃OCH₂Ph,

 CF₃(CF₃CF₂CF₂O)CFCOO(CH₂)₃OCH₂CH═CH₂,

 CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCF₂CF₂CF₃)CF₃,

CF₃CF₂COOCF₂CF₂CF₃,

CF₃CF₂COOCF₂CF₂CFClCF₂Cl,

CF₂ClCFCF₂CFClCOOCF₂CF₂CFClCF₂Cl,

CF₂ClCF₂CFClCOOCF₂CF₂CFClCF₂Cl,

CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCF₂CF₂CFClCF₂Cl)CF₃,

CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCF₂Cy^(F))CF₃,

CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(O(CF₂)₉CF₃)CF₃,

CF₃(CF₃CF₂CF₂O)CFCOO(CF₂)₃OCF₂Cy^(F),

CF₃(CF₃CF₂CF₂O)CFCOO(CF₂)₃OCF₂CF₂CF₃,

 FCOCF(O(CF₂)₉CF₃)CF₃

FCO(CF₂)₂OCF₂CY^(F).

BEST MODE FOR CARRYING OUT THE INVENTION

Description of Groups Disclosed in the Specification

In the present specification, a monovalent organic group means amonovalent group which essentially comprises carbon atoms. Themonovalent organic group may or may not contain fluorine atoms orhydrogen atoms. The carbon number of the monovalent organic group ispreferably from 1 to 20, particularly preferably from 1 to 10, from theviewpoint of the solubility in a liquid phase at the time of thefluorination reaction.

In the present specification, the monovalent hydrocarbon group may be amonovalent aliphatic hydrocarbon group or a monovalent aromatichydrocarbon group, and a monovalent aliphatic hydrocarbon group ispreferred. The structure of the monovalent aliphatic hydrocarbon groupmay, for example, be a straight chain structure, a branched structure, acyclic structure or a structure having a partially cyclic structure. Inthe monovalent aliphatic hydrocarbon group, a single bond, a double bondor a triple bond may be present as a carbon-carbon bond. When themonovalent aliphatic hydrocarbon group is a monovalent saturatedaliphatic hydrocarbon group, an alkyl group, a cycloalkyl group or amonovalent saturated aliphatic hydrocarbon group having a cyclic moiety(such as a cycloalkyl group, a cycloalkylene group or a bicycloalkylgroup, a group having an aliphatic spiro structure, or a group havingsuch a group as a partial structure) may, for example, be mentioned, andan alkyl group is preferred. As the monovalent aromatic hydrocarbongroup, a phenyl group, an aryl group or such a group having asubstituent, is preferred.

As the halogen atom in the present specification, a fluorine atom, achlorine atom, a bromine atom or an iodine atom may be mentioned, and afluorine atom, a chlorine atom or a bromine atom is preferred.

Further, in the present specification, “halogeno” means that at leastone hydrogen atom present in a group is substituted by at least onehalogen atom selected from a fluorine atom, a chlorine atom, a bromineatom and an iodine atom. In the group of a halogeno group, a hydrogenatom may or may not be present.

The “partially halogeno” means that a hydrogen atom which is notsubstituted by a halogen atom is present in the group of a halogenogroup. The “perhalogeno” means that no hydrogen atom is present in thegroup of a halogeno group.

In this specification, the halogeno monovalent hydrocarbon group may bea group having at least one hydrogen atom in the above-mentionedmonovalent hydrocarbon group substituted by a halogen atom. As such ahalogeno monovalent hydrocarbon group, a halogeno alkyl group ispreferred. As the halogen atom in the halogeno alkyl group, a fluorineatom, a chlorine atom or a bromine atom is preferred. Further, as apartially halogeno monovalent hydrocarbon group, a partially halogenoalkyl group is preferred. As the perhalogeno monovalent hydrocarbongroup, a perhalogeno alkyl group is preferred. The halogen atoms in aperhalogeno alkyl group are preferably composed of fluorine atoms onlyor fluorine atoms and halogen atoms other than fluorine atoms. Asspecific examples of these groups, groups disclosed in the followingexamples of compounds may be mentioned.

In the present specification, the hetero atom-containing monovalentsaturated hydrocarbon group may be a group containing in theabove-mentioned monovalent saturated hydrocarbon a hetero atom whichundergoes no change by the fluorination reaction or a hetero atom groupwhich undergoes no change by the fluorination reaction. Particularlypreferred is a group containing in a monovalent saturated hydrocarbongroup a bivalent hetero atom or a bivalent hetero atom group whichundergoes no change by the fluorination reaction.

The bivalent hetero atom which undergoes no change by the fluorinationreaction is preferably an etheric oxygen atom, and the bivalent heteroatom group which undergoes no change by the fluorination reaction may,for example, be —C(═O)— or —SO₂—.

As the hetero atom-containing monovalent saturated hydrocarbon group, analkyl group containing an etheric oxygen atom, or a monovalent aliphatichydrocarbon group having a cyclic portion having an etheric oxygen atominserted between carbon-carbon atoms, is preferred. Particularlypreferred is an alkoxyalkyl group.

Further, the halogeno(hetero atom-containing monovalent saturatedhydrocarbon) group may be a group having at least one hydrogen atom inthe above-mentioned hetero atom-containing monovalent saturatedhydrocarbon group substituted by a halogen atom, and ahalogeno(alkoxyalkyl) group is preferred.

In the compound (I), R^(A) is a monovalent saturated hydrocarbon group,a halogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, ahalogeno(hetero atom-containing monovalent saturated hydrocarbon) groupor a monovalent organic group (R^(H)) which can be converted to R^(HF)by a liquid-phase fluorination reaction.

And, R^(HF) is a group having at least one hydrogen atom in a groupselected from a monovalent saturated hydrocarbon group, a partiallyhalogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group and a partiallyhalogeno(hetero atom-containing monovalent hydrocarbon) group,substituted by a fluorine atom.

When R^(A) is a monovalent organic group (R^(H)), a specific example ofsuch a group is a group (R^(H1)) having a fluorine atom in the desiredR^(HF) substituted by a monovalent hetero atom group which can beconverted to a fluorine atom by a fluorination reaction, or a group(R^(H2)) having at least one carbon-carbon single bond in the desiredR^(HF) substituted by a carbon-carbon double bond or a carbon-carbontriple bond. Further, it is preferred that a hydrogen atom or a fluorineatom is bonded to the carbon atom which forms the carbon-carbon doublebond or the carbon-carbon triple bond in RH².

Here, the monovalent hetero atom group which can be converted to afluorine atom by a fluorination reaction may be a carboxyl group.Further, the group (R^(H2)) may, for example, be a cyclohexenyl group, aphenyl group, an alkenyl group or an alkynyl group. By a fluorinationreaction in a liquid phase, such R^(H2) becomes a carbon-carbon singlebond by an addition of fluorine atoms to the carbon atoms forming anunsaturated bond. For example, by the fluorination reaction, the phenylgroup becomes a perfluorocyclohexyl group.

Explanation About Compound (I)

In the compound (I), E¹ is a reactive group which is capable of forminga bivalent connecting group (E) by a reaction with E². Such a bivalentconnecting group (E) may be a group which changes or does not change bysuch a reaction.

As the bivalent connecting group (E), an ester bond-containing groupsuch as —CH₂OCO— or —CH₂OSO₂— (provided that the orientation of thesegroups is not limited). Particularly preferred is —CH₂OCO— from theviewpoint of usefulness of the resulting compound. With respect to E¹and E² in a case where E is an ester bond-containing group, one of themmay be —CH₂OH, and the other may be —COX (where X is a halogen atom) or—SO₂X. Now, a detailed description will be made with reference to a casewhere the bivalent connecting group (E) is —CH₂OCO—.

In the present invention, it is possible to employ various compoundsdiffering in the structure of R^(A), as the compound (I). Namely, bycarrying out the reaction of the present invention by using a compound(I) having a group (R^(A)) corresponding to R^(AF) in the desiredcompound (V), it is possible to produce a compound (V) which used to bedifficult to obtain by a conventional method. Likewise, variouscompounds differing in the structure of R^(B) can be employed as thecompound (II). As an example of the compound (V) which used to bedifficult to obtain by a conventional method, a compound wherein thestructure of R^(AF) is complex, or a fluorinated product of a lowmolecular weight whereby various types of by-products tend to form bythe fluorination reaction, may be mentioned. As an example of thelatter, a fluorinated product of one wherein the molecular weight of thecompound (I) is less than 200, preferably one wherein the molecularweight is from 50 to 200, may be mentioned.

The compound (I) is preferably a compound (Ia) wherein E¹ is —CH₂OH,particularly preferably a compound (Ia-1) wherein R^(A) is R^(AH),especially preferably a compound (Ia-2) wherein R^(A) is R¹:

R^(A)CH₂OH (Ia)

R^(AH)CH₂OH (Ia-1)

R¹CH₂OH (Ia-2)

Here, R^(A) has the same meaning as the meaning in the compound (I).R^(AH) is a monovalent saturated hydrocarbon group, a halogenomonovalent saturated hydrocarbon group, a hetero atom-containingmonovalent saturated hydrocarbon group or a halogeno(heteroatom-containing monovalent saturated hydrocarbon) group. R¹ is an alkylgroup, an alkoxyalkyl group, a halogenoalkyl group or ahalogeno(alkoxyalkyl) group.

When R¹ is an alkyl group, it is preferably a C₁₋₂₀ alkyl group,particularly preferably a C₁₋₁₀ alkyl group. The alkyl group may be of astraight chain structure, a branched structure, a cyclic structure or apartially cyclic structure. The alkyl group of a straight chainstructure may, for example, be a methyl group, an ethyl group, a propylgroup or a butyl group. The alkyl group of a branched structure may, forexample, be an isopropyl group, an isobutyl group, a sec-butyl group ora tert-butyl group.

When R¹ is an alkoxyalkyl group, it is preferably a group having atleast one hydrogen atom present in the above-mentioned alkyl groupsubstituted by an alkoxy group. The carbon number of such an alkoxygroup is preferably from 1 to 8. Such an alkoxyalkyl group may, forexample, be an ethoxymethyl group, a 1-propoxyethyl group or a2-propoxyethyl group.

When R¹ is a halogenoalkyl group, halogen atoms may be of one type ortwo or more types, and chlorine atoms, bromine atoms, or chorine atomsand bromine atoms, are preferred. As a specific example of such a group,a chloromethyl group, a bromomethyl group, a 2,3-dichloropropyl group ora 3,4-dichlorobutyl group may be mentioned.

When R¹ is a halogeno(alkoxyalkyl) group, halogen atoms may be of onetype or two or more types, and chlorine atoms, bromine atoms, orchlorine atoms and bromine atoms, are preferred. As a specific exampleof such a group, a 1-(3,4-dichlorobutoxy)ethyl group or a1-(2-bromoethoxy)ethyl group may be mentioned.

Further, the compound (Ia-2) is preferably one wherein R¹ is R⁴(R⁵O)CH—(wherein each of R⁴ and R⁵ which are independent of each other, is analkyl group or a halogenoalkyl group), a 2,3-dichloropropyl group or anethyl group, from the viewpoint of usefulness of the product. Namely,the compound (Ia-2) is preferably a compound (Ia-3),3,4-dichloro-1-butanol or 1-propanol.

R⁴(R⁵O)CHCH₂OH (Ia-3)

The compound (Ia-3) is preferably 2-propoxy-1-propanol[(CH₃)(CH₃CH₂CH₂O)CHCH₂OH] where R⁴ is a methyl group, and R⁵ is an-propyl group.

The following compounds may be mentioned as specific examples of thecompound (I). In the following, Cy is a cyclohexyl group, and Ph is aphenyl group.

CH₃(CH₃CH₂CH₂O)CHCH₂OH,

CH₃(CH₂ClCHClCH₂CH₂O)CHCH₂OH,

CH₃(BrCH₂CH₂O)CHCH₂OH,

CH₃[CH₂ClCHClCH₂CH(CH₃)O]CHCH₂OH,

CH₃CH₂CH₂OH,

CH₂═CHCH₂OH,

CH₂ClCHClCH₂CH₂OH,

CH₂ClCH₂OH,

CH₂BrCH₂OH,

CyCH₂OCH(CH₃)CH₂OH,

PhCH₂OCH(CH₃)CH₂OH,

CH₃(CH₂)₉OCH(CH₃)CH₂OH,

PhCH₂O(CH₂)₂CH₂OH,

CH₂═CHCH₂O(CH₂)₂CH₂OH,

CH₃CH₂CH₂OCH₂CH(CH₃)OH,

CF₂ClCFClCH₂CH₂OH,

The compound (Ia) is a compound which is readily available or which canreadily be synthesized by a known method. For example,3,4-dichloro-1-butanol can easily be synthesized by a known methoddisclosed in e.g. U.S. Pat. No. 4,261,901. Further, 2-alkoxyalcohols canbe easily synthesized by known methods disclosed, for example, in J. Am.Chem. Soc., 49, 1080(1927), Bull. Soc. Chim. Fr., 1813(1960), Can. J.Chem., 43, 1030(1965), Synthesis, 280(1981). 3-Alkoxyalcohols can easilybe synthesized by known methods disclosed, for example, in TetrahedronLett., 36,9161(1995), J. Org. Chem., 62, 7439(1997). Alcohols having adioxolane skeleton can easily be synthesized by known methods disclosed,for example, in Bull. Chem. Soc. Jpn., 70, 2561(1997).

Explanation About the Compound (II)

The compound (I) is reacted with the compound (II). In the compound(II), R^(B) is a monovalent saturated hydrocarbon group, a halogenomonovalent saturated hydrocarbon group, a hetero atom-containingmonovalent saturated hydrocarbon group, a halogeno(heteroatom-containing monovalent saturated hydrocarbon) group, or a monovalentorganic group (R^(H)) which can be converted to R^(HF) by a fluorinationreaction in a liquid phase, and embodiments of these groups are the sameas R^(A). With respect to R^(B), its structure is preferably adjusted inrelation with the structure of R^(A), so that the resulting compound(III) will be readily soluble in a liquid phase to be used at the timeof fluorination.

Further, in the present invention, it is preferred that one or each ofR^(A) and R^(B) is a monovalent organic group containing fluorine atoms.Further, the fluorine content in the compound (III) (the proportion offluorine atoms in the molecule) is preferably suitably changed dependingupon the type of the liquid phase to be used for the fluorinationreaction. Usually, the fluorine content is preferably at least 10 mass%, particularly preferably from 10 to 86 mass %, especially preferablyfrom 10 to 76 mass %, and further preferably from 30 to 76 mass %. It ispreferred to select R^(A) and R^(B) so that the fluorine content will bewithin such a range.

R^(A) may be a group which contains or does not contain fluorine atoms.Whereas, R^(B) is preferably a perhalogeno group, particularlypreferably a perfluoro group, since the after-mentioned continuousprocess can easily be carried out.

The compound (II) may be a commercial product or the compound (VI)formed by the after-described method of the present invention.

As described above, E² in the compound (II) is preferably —COX or —SO₂X(wherein X is a halogen atom, preferably a chlorine atom or a fluorineatom, and when a continuous process is carried out, X is preferably afluorine atom), particularly preferably —COX.

Namely, the compound (II) is preferably a compound (IIb) wherein E² is—COF, particularly preferably a compound (IIb-1) wherein R^(B) isR^(BF1), especially preferably a compound (IIb-2) wherein R^(B) is R².

FCOR^(B) (IIb) FCOR^(BF1) (IIb-1) FCOR² (IIb-2)

Here, R^(B) has the same meaning as the meaning in the compound (II).R^(BF1) is a perhalogeno monovalent saturated hydrocarbon group or aperhalogeno(hetero atom-containing monovalent saturated hydrocarbon)group. R² is a perhalogenoalkyl group or a perhalogeno(alkoxyalkyl)group.

R^(BF1) is preferably R^(BF10) (wherein R^(BF10) is a perfluoromonovalent saturated hydrocarbon group, a perfluoro(partiallychlorinated monovalent saturated hydrocarbon) group, a perfluoro(heteroatom-containing monovalent saturated hydrocarbon) group or aperfluoro(partially chlorinated hetero atom-containing monovalentsaturated hydrocarbon) group).

The halogen atom in R² is preferably a fluorine atom, a chlorine atom ora bromine atom. Further, halogen atoms in R² may be of one type or twoor more types, and particularly preferred is a case where all of thehalogen atoms in R² are fluorine atoms, or 1 or 2 halogen atoms in R²are chlorine atoms or bromine atoms and all of other halogen atoms arefluorine atoms. R² is preferably a perfluoroalkyl group, aperfluoro(partially chlorinated alkyl) group, a perfluoro(alkoxyalkyl)group or a perfluoro(partially chlorinated alkoxyalkyl) group.

When R² is a perhalogenoalkyl group, the carbon number is preferablyfrom 1 to 20, particularly preferably from 1 to 10. Such a group may beof a straight chain structure or a branched structure. When theperhalogenoalkyl group is of a straight chain structure, it may, forexample, be —CF₃, —CF₂CF₃, —CF₂CF₂CF₃, —CF₂CF₂CF₂CF₃, —CClF₂, —CBrF₂ or—CF₂CFClCF₂Cl. When the perhalogeno alkyl group is of a branchedstructure, it may, for example, be —CF(CF₃)₂, —CF₂CF(CF₃)₂,—CF(CF₃)CF₂CF₃ or —C(CF₃)₃.

When R² is a perhalogeno(alkoxyalkyl) group, the structure of thealkoxyalkyl group moiety is preferably a structure having one hydrogenatom present in a C₁₋₂₀ (preferably C₁₋₁₀) alkyl group substituted by aC₁₋₈ alkoxy group.

As an example of a case where R² is a perhalogeno(alkoxyalkyl) group,—CF(OCF₂CF₂CF₃)CF₃, —CF(OCF₂CF₂CFClCF₂Cl)CF₃ or —CF(OCF₂CF₂Br)CF₃ may,for example, be mentioned.

From the usefulness of the product, the compound (IIb-2) is preferablythe following compound (IIb-3) (wherein each of R⁸ and R⁹ which areindependent of each other, is a perhalogenoalkyl group), a compound(IIb-2) wherein R² is —CF₂CFClCF₂Cl, or CF₃CF₂COF.

FCOCFR⁸(OR⁹) (IIb-3)

The following compounds may be mentioned as specific examples of thecompound (II):

CF₃CF₂COF,

CF₂ClCFClCF₂COF,

CF₂ClCF₂CFClCOF,

CF₃(CF₃CF₂CF₂O) CFCOF,

CF₃(CF₂ClCFClCF₂CF₂O) CFCOF,

CClF₂COF,

CBrF₂COF,

CF₃(CF₂BrCF₂O)CFCOF,

CF₃[CF₂ClCFClCF₂CF(CF₃)O]CFCOF,

CF₃CF₂CF₂OCF(CF₃)CF₂OCF(CF₃)COF,

CF₃(CH₃CH₂CH₂O)CFCOF,

CH₂ClCHClCH₂COCl.

As the compound (II), CF₃(CF₃CF₂CF₂O)CFCOF is particularly preferred.This compound can be readily available as an intermediate for aperfluoro(alkyl vinyl ether).

The reaction of the compound (I) with the compound (II) can be carriedout by applying known reaction methods and conditions depending upon thestructures of E¹ and E² and their combination. For example, the reactionof the compound (Ia) wherein E¹ is —CH₂OH with a compound (IIb) whereinE² is —COX, can be carried out under known reaction conditions. Suchreaction may be carried out in the presence of a solvent (hereinafterreferred to as solvent 1), but it is preferred to carry out the reactionin the absence of solvent 1, from the viewpoint of the volumeefficiency. In a case where solvent 1 is used, dichloromethane,chloroform, triethylamine or a solvent mixture of triethylamine withtetrahydrofuran, is preferred. The amount of solvent 1 is preferablyfrom 50 to 500 mass %, based on the total amount of the compound (Ia)and the compound (IIb).

In the reaction of the compound (Ia) with the compound (IIb), an acidrepresented by HX will be formed. When a compound wherein X is afluorine atom is used as the compound (IIb), HF will be formed, and as acapturing agent for HF, an alkali metal fluoride (preferably NaF or KF)or a trialkylamine may be present in the reaction system. It ispreferred to use a capturing agent for HF, when the compound (Ia) or thecompound (IIb) is a compound which is unstable against an acid. Further,when a capturing agent for HF is not used, it is preferred to dischargeHF out of the reaction system as accompanied in a nitrogen stream. Whenan alkali metal fluoride is employed, its amount is preferably from 1 to10 mol times, based on the compound (IIb).

The temperature for the reaction of the compound (Ia) with the compound(IIb) is usually preferably at least −50° C., and preferably at most+100° C. or at most the boiling point temperature of the solvent.Further, the reaction time of such a reaction may be suitably changeddepending upon the supply rates of the starting materials and theamounts of the compounds to be used for the reaction. The reactionpressure (gauge pressure, the same applies hereinafter) is preferablyfrom atmospheric pressure to 2 MPa.

Explanation About the Compound (III)

By the reaction of the compound (I) with the compound (II), a compound(III) will be formed. In the compound (III), R^(A) is the same group asR^(A) in the compound (I), and R^(B) is the same group as R^(B) in thecompound (II). E is a bivalent connecting group formed by the reactionof E¹ with E², and the above-mentioned groups may be mentioned. Themolecular weight of the compound (III) is preferably from 200 to 1000,whereby the fluorination reaction in a liquid phase can be smoothlycarried out. If the molecular weight is too small, the compound (III)tends to be readily volatile, and it is likely that a decompositionreaction may take place in a gas phase during the fluorination reactionin a liquid phase. On the other hand, if the molecular weight is toolarge, purification of the compound (III) tends to be difficult.

Further, the fluorine content in the compound (III) is preferably theabove-mentioned amount. The compound (III) is preferably a compound(IIIc) which is formed by the reaction of the compound (Ia) with thecompound (IIb), particularly preferably a compound (IIIc-1) which isformed by the reaction of the compound (Ia-1) with the compound (IIb-1),especially preferably a compound (IIIc-2) which is formed by thereaction of a compound (Ia-2) with a compound (IIb-2):

R^(A)CH₂OCOR^(B) (IIIc) R^(AH)CH₂OCOR^(BF1) (IIIc-1) R¹CH₂OCOR² (IIIc-2)

wherein R^(A), R^(B), R^(AH), R^(BF1), R¹ and R² have the same meaningsas described above, and the preferred embodiments are also the same.

The compound (IIIc-2) is preferably a compound (IIIc-20) wherein R¹ isR⁴ (R⁵O)CH—, a compound (IIIc-21) wherein R² is —CFR⁸(OR⁹), orCF₃CF₂COOCH₂CH₂CH₃ wherein R¹ is an ethyl group, and R² is apentafluoroethyl group. Further, the compound (IIIc-2) is preferably acompound (IIIc-3) wherein R¹ is R⁴(R⁵O)CH—, and R² is —CFR⁸(OR⁹),especially preferably a compound (IIIc-30):

R⁴(R⁵O)CHCH₂OCOR² (IIIc-20) R¹CH₂OCOCFR⁸(OR⁹) (IIIc-21)R⁴(R⁵O)CHCH₂OCOCFR⁸(OR⁹) (IIIc-3) CH₃(CH₃CH₂CH₂O)CHCH₂OCOCFR⁸(OR⁹) (IIIc-30)

The following compounds may be mentioned as specific examples of thecompound (III):

CF₃CF₂COOCH₂CH₂CH₃,

CF₃CF₂COOCH₂CH(OCH₂CH₂CH₃)CH₃,

CF₃CF₂COOCH₂CH(OCH₂CH₂CHClCH₂Cl)CH₃,

CF₃CF₂COO(CH₂)₄OCHClCH₂Cl,

CF₃CF₂COO(CH₂)₅OCHClCH₂Cl,

CF₃(CF₃CF₂CF₂O)CFCOO(CH₂)₄OCHClCH₂Cl,

CF₃(CF₃CF₂CF₂O)CFCOO(CH₂)₅OCHClCH₂Cl,

CF₃(CF₂ClCFClCF₂CF₂O)CFCOOCH₂CH(OCH₂CH₂CHClCH₂Cl)CH₃,

CF₂ClCFClOCF₂CF₂CF₂COO(CH₂)₄OCHClCH₂Cl,

CClF₂COOCH₂CH₂Cl,

CBrF₂COOCH₂CH₂Br,

CF₂BrCF₂OCF(CF₃COOCH₂CH(OCH₂CH₂Br) CH₃,

CF₂ClCFClCF₂CF(CF₃)OCF(CF₃)COOCH₂CH[OCH(CH₃)CHClCH₂Cl]CH₃,

CH₂ClCHClCH₂COOCH₂CF₂CFClCF₂Cl,

CF₃(CH₃CH₂CH₂O)CFCOOCH₂CF(OCF₂CF₂CF₃)CF₃,

CF₃(CH₃CH₂CH₂O)CFCOOCH₂CF(OCH₂CH₂CH₃)CF₃,

CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂CH₂CH₃)CH₃,

CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂CH₂CHClCH₂Cl)CH₃,

CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂Cy)CH₃,

CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂Ph)CH₃,

CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(O(CH₂)₉CH₃)CH₃,

CF₃(CF₃CF₂CF₂O)CFCOO(CH₂)₃OCH₂Ph,

CF₃(CF₃CF₂CF₂O)CFCOO(CH₂)₃OCH₂CH═CH₂,

CF₃CF₂COOCH₂CH₂CHClCH₂Cl,

CF₂ClCFClCF₂COOCH₂CH₂CHClCH₂Cl,

CF₂ClCF₂CFClCOOCH₂CH₂CHClCH₂Cl,

The above-mentioned novel compound (III) is useful as an intermediatefor a fluorinated resin material, and can be led to a fluorinated resinmaterial by the after-described reaction. Especially in the novelcompound (III), a compound having —CHClCH₂Cl at its molecular terminalscan be led to a fluorinated resin material having two polymerizableunsaturated groups.

A crude product containing the compound (III) formed by the reaction ofthe compound (I) with the compound (II), may be purified depending uponthe particular purpose or may be used for the next reaction as it is.With a view to carrying out the fluorination reaction of the next stepsafely, it is preferred that the compound (III) in the crude product isseparated and purified.

The purification method of the crude product may, for example, be amethod of distilling the crude product directly, a method of treatingthe crude product with a dilute alkali water, followed by liquidseparation, a method of extracting the crude product with a suitableorganic solvent, followed by distillation, or silica gel columnchromatography.

Explanation About the Compound (IVd)

Then, in the present invention, the compound (III) is fluorinated in aliquid phase to obtain a compound (IV). The fluorination in a liquidphase is preferably carried out by a method of fluorinating the compound(IIIc) in a solvent with fluorine gas (fluorination method-1) or byelectrochemical fluorination (fluorination method-2), particularlypreferably fluorination method-1.

When fluorination is carried out by fluorination method-2, it ispreferred that the compound (III) is dissolved in anhydrous hydrofluoricacid to obtain a solution, and this solution is electrolyzed in anelectrolytic cell to fluorinate the compound (III) to form a compound(IV).

When fluorination is carried out in fluorination method-1, the compound(III) and fluorine gas are reacted in a solvent (hereinafter referred toas solvent-2) to form a compound (IV). The fluorine gas may be used asit is, or fluorine gas diluted with an inert gas may be employed. As theinert gas, nitrogen gas or helium gas is preferred, and nitrogen gas isparticularly preferred from an economical reason. The amount of fluorinegas in the nitrogen gas is not particularly limited, and at least 10% ispreferred from the viewpoint of the efficiency, and at least 20% isparticularly preferred.

Solvent-2 to be used for fluorination method-1 is preferably a solventwhich contains no C—H bond and which necessarily contains a C—F bond.Further, a perfluoroalkane or an organic solvent obtained byperfluorinating a known organic solvent having at least one atomselected from a chlorine atom, a nitrogen atom and an oxygen atom in itsstructure, is preferred. Further, as solvent-2, it is preferred toemploy a solvent which provides a high solubility to the compound (III),and it is particularly preferred to employ a solvent which is capable ofdissolving at least 1 mass % of the compound (III), particularly asolvent which is capable of dissolving at least 5 mass %.

Examples of solvent-2 may be a compound (IIb-2), an after-describedcompound (IVd-2), perfluoroalkanes (such as FC-72), perfluoroethers(such as FC-75 and FC-77), perfluoropolyethers (tradenames: KRYTOX,FOMBLIN, GALDEN and Demnum), chlorofluorocarbons (tradename: Flon Lube),chlorofluoropolyesters, perfluoroalkylamines [such asperfluorotrialkylamine], and an inert fluid (tradename: Fluorinert).Among them, a perfluorotrialkylamine, the compound (V) or the compound(VI) (preferably the compound (IIb-2), the compound (IV) (preferably thecompound (IVd-2)) is preferred. Particularly when the compound (IV), thecompound (V) or the compound (VI) is employed, there will be a meritthat workup after the reaction will be easy. The amount of solvent-2 ispreferably at least five times by mass, particularly from 10 to 100times by mass, relative to the compound (III).

The reaction type of the fluorination reaction of fluorination method-1is preferably a batch system or a continuous system. Especially from theviewpoint of the reaction yield and selectivity, a continuous system (2)which will be described hereinafter, is preferred. Further, fluorine gasmay be one diluted with an inert gas such as nitrogen gas either whenthe reaction is carried out by a batch system or when it is carried outby a continuous system.

Continuous system (1) Into a reactor, the compound (III) and solvent-2are charged, and stirring is initiated. A method of reacting at apredetermined reaction temperature and reaction pressure while supplyingfluorine gas continuously.

Continuous system (2) Into a reactor, solvent-2 is charged, and stirringis initiated. A method of supplying the compound (III), solvent-2 andfluorine gas under a predetermined reaction temperature and reactionpressure in a predetermined molar ratio continuously and simultaneously.In the continuous system (2), when the compound (III) is supplied, it ispreferred to supply the compound (III) as diluted with solvent-2, toimprove the selectivity and to suppress the amount of by-products.Further, in the continuous system (2), when the compound (III) isdiluted with the solvent, it is preferred to adjust the amount ofsolvent-2 to at least five times by mass, particularly preferably atleast ten times by mass, relative to the compound (III).

With respect to the amount of fluorine to be used for the fluorinationreaction, when the reaction is carried out by a batch system, it ispreferred to charge fluorine gas so that the amount of fluorine atoms isalways excess equivalent, relative to hydrogen atoms in the compound(III), and it is particularly preferred that fluorine gas is used sothat it becomes at least 1.5 times by equivalent, from the viewpoint ofselectivity. Further, when the reaction is carried out by a continuousprocess, it is preferred to continuously supply fluorine gas so that theamount of fluorine atoms will be excess equivalent, relative to hydrogenatoms in the compound (III), and it is particularly preferred tocontinuously supply fluorine gas so that it becomes at least 1.5 timesby equivalent, relative to the compound (III), from the viewpoint ofselectivity.

The reaction temperature for the fluorination reaction by fluorinationmethod-1 may be varied depending upon the structure of the bivalentconnecting group (E), but it is usually preferably at least −60° C. andat most the boiling point of the compound (III), and from the viewpointof the reaction yield, the selectivity and efficiency for industrialoperation, it is particularly preferably from −50° C. to +100° C.,especially preferably from −20° C. to +50° C. The reaction pressure ofthe fluorination reaction is not particularly limited, and it isparticularly preferably from atmospheric pressure to 2 MPa from theviewpoint of the reaction yield, the selectivity and efficiency forindustrial operation.

Further, in order to let fluorination method-1 proceed efficiently, itis preferred to add a C—H bond-containing compound to the reactionsystem or to carry out in the presence of ultraviolet light. Forexample, in a batch system reaction, it is preferred to add a C—Hbond-containing compound to the reaction system or to carry out in thepresence of ultraviolet light at a later stage of the fluorinationreaction. In a continuous system reaction, it is preferred to add a C—Hbond-containing compound, or to carry out in the presence of ultravioletlight, whereby the compound (III) present in the reaction system canefficiently be fluorinated, and the reaction rate can remarkably beimproved. The time for ultraviolet irradiation is preferably from 0.1 to3 hours.

The C—H bond-containing compound is an organic compound other than thecompound (III), and an aromatic hydrocarbon is particularly preferred.Especially preferred is, for example, benzene or toluene. The amount ofsuch a C—H bond-containing compound is preferably from 0.1 to 10 mol %,particularly preferably from 0.1 to 5 mol %, relative to hydrogen atomsin the compound (III).

It is preferred to add the C—H bond-containing compound in such a statewhere fluorine gas is present in the reaction system. Further, when theC—H bond-containing compound is added, it is preferred to pressurize thereaction system. The pressure during the pressurizing is preferably from0.01 to 5 MPa.

In the fluorination reaction of the compound (III), a compound (IV) willbe formed. In the compound (IV), R^(AF) is a group corresponding toR^(A), and R^(BF) is a group corresponding to R^(B). In a case whereeach of R^(A) and R^(B) is a monovalent saturated hydrocarbon group, ahalogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group or ahalogeno(hetero atom-containing monovalent saturated hydrocarbon) group,each of R^(AF) and R^(BF) is the same group as R^(A) and R^(B),respectively, or a group having at least one hydrogen atom present inthe group of R^(A) or R^(B) substituted by a fluorine atom. R^(AF) andR^(BF) are preferably groups which are substituted by fluorine, and insuch groups, non-substituted hydrogen atoms may be present. The amountsof hydrogen atoms in such groups are preferably suitably changeddepending upon the particular purpose.

Further, when a compound (III) wherein hydrogen atoms are present inR^(A) and R^(B), is fluorinated, R^(AF) and R^(BF) in the compound (IV)to be formed, may be groups wherein He hydrogen atoms may or may not bepresent, preferably groups wherein no hydrogen atoms are present,particularly preferably groups wherein all of hydrogen atoms in R^(A)and R^(B) are substituted by fluorine atoms.

Further, in a case where even if hydrogen atoms are present in R^(A) andR^(B), such hydrogen atoms are not susceptible to fluorination, or in acase where a compound (III) wherein R^(A) and R^(B) are perhalogenogroups, is employed, R^(AF) and R^(BF) in the compound (IV) are the samegroups as R^(A) and R^(B), respectively. In a case where R^(A) and R^(B)are monovalent organic groups (R^(H)), R^(AF) and R^(BF) are R^(HF)corresponding to such R^(H), respectively.

In the fluorination reaction in a liquid phase, it is difficult toadjust the position for introduction of a fluorine atom, andaccordingly, R^(AF) and R^(BF) in the compound (IV) are preferablygroups which contain no hydrogen atoms. Namely, when a compound (III)wherein each of R^(A) and R^(B) is a group containing hydrogen atoms, isemployed, it is preferred to obtain a compound (IV) having R^(AF) andR^(BF) wherein all of such hydrogen atoms are substituted by fluorineatoms.

Each of R^(AF) and R^(BF) is preferably a perfluoro monovalent saturatedhydrocarbon group, a perfluoro(partially halogeno monovalent saturatedhydrocarbon) group, a perfluoro(hetero atom-containing monovalentsaturated hydrocarbon) group, or a perfluoro[partially halogeno(heteroatom-containing monovalent saturated hydrocarbon)] group.

E^(F) is the same group as E, or a group having E fluorinated. Anexample of the latter group may be a group having at least one hydrogenatom present in E fluorinated, or in a case where a —CH═CH— moiety ispresent in E, a group having fluorine atoms added to such moiety to form—CF₂CF₂—. Further, the compound (IV) is not of the same structure as thecompound (III), and at least one of R^(AF), R^(BF) and E^(F) is of astructure different from the corresponding R^(A), R^(B) and E,respectively. Namely, at least one of R^(A), R^(B) and E is a groupmodified by the fluorination reaction.

The compound (IV) is preferably a compound (IVd) which is formed byfluorination of a compound (III) wherein E is —CH₂OCO—, particularlypreferably a compound (IVd-1) which is formed by completely fluorinatingthe compound (IIIc-1), especially preferably a compound (IVd-2) which isformed by completely fluorinating the compound (IIIc-2):

R^(AF)CF₂OCOR^(BF) (IVd) R^(AF1)CF₂OCOR^(BF1) (IVd-1) R³CF₂OCOR² (IVd-2)

wherein R^(AF) and R^(BF): the same meanings as the meanings in thecompound (IV);

R^(AF1): R^(AF1) is a group corresponding to R^(AH), and when R^(AH) isa group containing hydrogen atoms, a group having all of hydrogen atomsin such a group substituted by fluorine atoms, and when R^(AH) is agroup containing no hydrogen atom, the same group as R^(AH);

R^(BF1): A perhalogeno monovalent saturated hydrocarbon group or aperhalogeno(hetero-atom-containing monovalent saturated hydrocarbon)group;

R³: A group corresponding to R¹, and when R¹ is a group containing nohydrogen atom, the same group as R¹, and when R¹ is a group containinghydrogen atoms, a group having all of hydrogen atoms in such a groupsubstituted by fluorine atoms;

R²: The same group as R² in (IIIc-2).

Further, from the viewpoint of usefulness, the compound (IVd-2) ispreferably a compound (IVd-20) where R³ is R⁶(R⁷O)CF—, a compound(IVd-21) where R² is —CFR⁸(OR⁹), or perfluoro(propyl propionate) whereR² and R³ are perfluoroethyl groups:

R⁶(R⁷O)CFCF₂ OCOR²(IVd-20) R³CF₂OCOCFR⁸(OR⁹) (IVd-21)

wherein R², R³: The same meanings as described above;

R⁶: A group corresponding to R⁴, and when R⁴ is a group containing nohydrogen atom, the same group as R⁴ ₁ and when R⁴ is a group containinghydrogen atoms, a group having all of hydrogen atoms in such a groupsubstituted by fluorine atoms;

F⁷: A group corresponding to R⁵, and when R⁵ is a group containing nohydrogen atom, the same group as R⁵, and when R⁷ is a group containinghydrogen atoms, a group having all of hydrogen atoms in such a groupsubstituted by fluorine atoms;

R⁸, R⁹: The same meanings as described above.

Further, the compound (IVd-2) is preferably a compound (IVd-3) where R³is R⁶(R⁷O)CF—, and R² is —CFR⁸(OR⁹). Such compound (IVd-3) can beproduced by the following production route. Namely, it is obtainable byreacting the compound (Ia-3) with the compound (IIb-3) to form acompound (IIIc-3) and fluorinating the compound (IIIc-3) in a liquidphase (preferably by reacting with fluorine gas in a solvent). Thesymbols in the following formulae have the same meanings as describedabove.

R⁴(R⁵O)CHCH₂OH(Ia-3)+FCOCFR⁸(OR⁹) (IIb-3)→R⁴(R⁵O)CHCH₂OCOCFR⁸(OR⁹)(IIIc-3)→R⁶ (R⁷O) CFCF₂OCOCFR⁸(OR⁹) (IVd-3)

The following compounds may be mentioned as specific examples of thecompound (IV):

CF₃CF₂COOCF₂CF(OCF₂CF₂CF₃)CF₃,

CF₃CF₂COOCF₂CF(OCF₂CF₂CFClCF₂Cl)CF₃,

CF₃(CF₂ClCFClCF₂CF₂O)CFCOOCF₂CF(OCF₂CF₂CFClCF₂Cl)CF₃,

CClF₂COOCF₂CF₂Cl,

CBrF₂COOCF₂CF₂Br,

CF₃(CF₂BrCF₂O)CFCOOCF₂CF(OCF₂CF₂Br)CF₃,

CF₃[CF₂ClCFClCF₂CF(CF₃)O]CFCOOCF₂CF[OCF(CF₃)CF₂CFClCF₂Cl ]CF₃,

CF₃CF₂COOCF₂CF(OCHFCF₂CFClCF₂Cl)CF₃,

CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCHFCF₂CFClCF₂Cl)CF₃,

CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCF₂CF₂CF₃)CF₃,

CF₃CF₂COOCF₂CF₂CF₃,

CF₃CF₂COOCF₂CF₂CFClCF₂Cl,

CF₂ClCFClCF₂COOCF₂CF₂CFClCF₂Cl,

CF₂ClCF₂CFClCOOCF₂CF₂CFClCF₂Cl,

CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCF₂CF₂CFClCF₂Cl)CF₃.

CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCF₂CY^(F))CF₃,

CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(O(CF₂)₉CF₃)CF₃,

CF₃(CF₃CF₂CF₂O)CFCOO(CF₂)₃OCF₂CY^(F),

CF₃(CF₃CF₂CF₂O)CFCOO(CF₂)₃OCF₂CF₂CF₃,

In the liquid-phase fluorination reaction of the compound (III), when areaction to substitute hydrogen toms with fluorine atoms takes place, HFwill be formed as a by-product. To remove HF formed as a by-product, itis preferred to incorporate an HF scavenger in the reaction system or tocontact the outlet gas with an HF scavenger at the gas outlet of thereactor. As such an HF scavenger, the same as described above may beemployed, and NaF is preferred.

When the HF scavenger is incorporated in the reaction system, the amountis preferably from 1 to 20 mol times, more preferably from 1 to 5 moltimes, relative to the total amount of hydrogen atoms present in thecompound (III). In a case where the HF scavenger is disposed at theoutlet of the reactor, it is preferred to arrange (1) a condenser(preferably maintained at a temperature of from 10° C. to roomtemperature, particularly preferably at about 20° C.) (2) a NaF pelletpacked layer and (3) a condenser (preferably maintained at a temperatureof from −78° C. to +10° C., more preferably from −30° C. to 0° C.) in aseries in the order of (1)-(2)-(3). Further, a liquid-returning line maybe installed to return the condensed liquid from the condenser of (3) tothe reactor.

The crude product containing the compound (IV) obtained by thefluorination reaction may be employed for the next step as it is or maybe purified to a high purity. The purification method may, for example,be a method of distilling the crude product as it is under atmosphericpressure or reduced pressure.

Explanation About the Compound (Ve)

In the present invention, the compound (IV) is further converted to acompound (V). Such a conversion reaction is a reaction to dissociateE^(F) in the compound (IV) into E^(F1) and E^(F2). The method andconditions of the conversion reaction may suitably be changed dependingupon the structure of the compound (IV). In a case where the compound(IV) is a compound (IVd), the conversion reaction is a reaction todissociate —CF₂OCO—.

The conversion reaction of the compound (IVd) is preferably carried outby a thermal decomposition reaction or a decomposition reaction which iscarried out in the presence of a nucleophile or an electrophile. By sucha reaction, a compound (Ve) and the compound (VIf) wherein E^(F1) andE^(F2) are —COF, will be formed.

The thermal decomposition reaction can be carried out by heating thecompound (IVd). The reaction type of the thermal decomposition reactionis preferably selected from the boiling point and the stability of thecompound (IVd). For example, when a compound (IVd) which is readilyvaporized, is to be thermally decomposed, a gas phase thermaldecomposition method may be employed in which it is continuouslydecomposed in a gas phase, and the outlet gas containing the obtainedcompound (Ve) is condensed and recovered.

The reaction temperature of the gas phase thermal decomposition methodis preferably from 50 to 350° C., particularly preferably from 50 to300° C., especially preferably from 150 to 250° C. Further, an inert gaswhich is not concerned directly with the reaction, may be present in thereaction system. As such an inert gas, nitrogen or carbon dioxide may,for example, be mentioned. It is preferred to add an inert gas in anamount of from 0.01 to 50 vol % relative to the compound (IVd). If theamount of the inert gas is large, the recovery of the product maysometimes decrease. The method and conditions of the gas phasedecomposition method can be applied to any compound contained in thescope of the compound (IVd).

On the other hand, in a case where the compound (IV) is a compound whichis hardly vaporized, it is preferred to employ a liquid phase thermaldecomposition method wherein it is heated in the state of a liquid inthe reactor. The reaction pressure in this case is not limited. In ausual case, the product containing the compound (Ve) is of a lowerboiling point, and it is preferred to obtain the product by a method ofa reaction distillation type wherein the product is vaporized andcontinuously withdrawn. Otherwise, it may be a method wherein aftercompletion of the heating, the product is withdrawn all together fromthe reactor. The reaction temperature for this liquid phase thermaldecomposition method is preferably from 50 to 300° C., particularlypreferably from 100 to 250° C.

When the thermal decomposition is carried out by the liquid phasethermal decomposition method, the decomposition may be carried out inthe absence of a solvent or in the presence of a solvent (hereinafterreferred to as solvent-3). Solvent-3 is not particularly limited so longas it is not reactive with the compound (IVd) and it is compatible withthe compound (IVd) and is not reactive with the resulting compound (Ve).Further, as solvent-3, it is preferred to select one which is readilyseparable at the time of purification of the compound (Ve). A specificexample of solvent-3 may be an inert solvent such asperfluorotrialkylamine or perfluoronaphthalene, or a chlorofluorocarbon,particularly preferably chlorotrifluoroethylene oligomer having a highboiling point (for example, tradename: Flon Lube). Further, the amountof solvent-3 is preferably from 10 to 1000 mass % relative to thecompound (IVd).

Further, in a case where the compound (IVd) is decomposed by reacting itwith a nucleophile or an electrophile in a liquid phase, such a reactionmay be carried out in the absence of a solvent or in the presence of asolvent (hereinafter referred to as solvent-4). Solvent-4 is preferablythe same as solvent-3. The nucleophile is preferably a fluoride anion(F⁻), particularly preferably a fluoride anion derived from an alkalimetal fluoride. The alkali metal fluoride is preferably NaF, NaHF₂, KFor CsF. Among them, NaF is particularly preferred from the viewpoint ofeconomical efficiency.

When the nucleophile such as (F⁻) is employed, F⁻ is nucleophilicallyadded to a carbonyl group present in the ester bond of the compound(IVd), whereby R^(AF)CF₂O⁻ will be detached, and an acid fluoride[compound (VIf)] will be formed. From R^(AF)CF₂O⁻, F⁻ will further bedetached to form an acid fluoride [compound (Ve)]. The detached F⁻ willreact with another molecule of the compound (VId) in the same manner.Accordingly, the nucleophile to be used at the initial stage of thereaction may be in a catalytic amount or may be used excessively.Namely, the amount of the nucleophile such as F⁻ is preferably from 1 to500 mol %, particularly preferably from 10 to 100 mol %, especiallypreferably from 5 to 50 mol %, relative to the compound (IVd). Thereaction temperature is preferably from −30° C. to the boiling point ofthe solvent or the compound (IVd), particularly preferably from −20° C.to 250° C. This method is also preferably carried out by thedistillation column type production method.

In the conversion reaction of the compound (IVd), the compound (Ve)and/or the compound (VIf) will be formed; in the conversion reaction ofthe compound (IVd-1), the compound (Ve-1) and/or the compound (VIf-1)will be formed; in the thermal decomposition of the compound (IVd-2),the compound (Ve-2) and/or the compound (IIb-2) will be formed; and inthe thermal decomposition of the compound (IVd-3), the compound (Ve-3)and/or the compound (VIe-3) will be formed.

R^(AF)COF (Ve) R^(BF)COF (VIf) R^(AF1)COF (Ve-1) R^(BF1)COF (VIf-1)R³COF (Ve-2) R²COF (IIb-2) R⁶(R⁷O)CFCOF (Ve-3) R⁸(R⁹O)CFCOF (VIe-3)

wherein the meanings of A^(F), B^(F), R², R³, R⁶ to R⁹ and R^(BF1) arethe same as the above meanings, and R^(AF1) is a group corresponding toR^(AH), and each represents a perhalogeno monovalent saturatedhydrocarbon group or a perhalogeno(hetero atom-containing monovalentsaturated hydrocarbon) group.

The following compounds may be mentioned as specific examples of thecompound (Ve):

 CF₃CF₂COF, CF₂ClCFClCF₂COF, CF₂ClCF₂CFClCOF, CF₃(CF₃CF₂CF₂O)CFCOF,CF₃(CF₂ClCFClCF₂CF₂O)CFCOF, CF₃(CF₂ClCFClCF₂CHFO)CFCOF.FCOCF(O(CF₂)₉CF₃)CF₃, FCO(CF₂)₂OCF₂Cy^(F),

Among the compound (Ve) and/or the compound (VIf) thereby obtainable, acompound having a partial structure of “C¹F—C²—COF” at the molecularterminals, can be led to a fluorine resin material by converting themolecular terminals to “C¹═C²” by a known reaction (Methods of OrganicChemistry, 4, Vol.10b, Part 1, p.703, etc.). Namely, the novel compound(Ve) and/or the compound (VIf) is a compound useful as a precursor for afluorinated resin material. Further, the novel compound (IIIc) andcompound (IVd) are compounds useful as intermediates for suchprecursors.

The novel compound presented by the present invention, can be led to auseful fluorinated resin material by a method which will be describedbelow. Namely, a compound (IIb) or a compound (IIIc) wherein R^(B) andR^(BF) are CF₃(CF₃CF₂CF₂O)CF—, can be led to a compound (IIb-30) whichis a precursor for a useful fluorinated resin material(CF₃CF₂CF₂OCF═CF₂) by the following route. For example, the productionroute wherein R^(B) and R^(BF) are CF₃(CF₃CF₂CF₂O)CF—, will berepresented as follows:

R^(A)CH₂OH+FOCOCF(OCF₂CF₂CF₃)CF₃→R^(A)CH₂OCOCF(OCF₂CF₂CF₃)CF₃→R^(AF)CF₂OCOCF(OCF₂CF₂CF₃)CF₃→R^(AF)COF+CF₃(CF₃CF₂CF₂O)CFCOF(IIb-30)→CF₃CF₂CF₂OCF═CF₂

Further, in a case where an unsaturated bond is present in R^(A) in thecompound (IIb) (for example, a phenyl is present in R^(A)), a product(IIb-30) will be obtained by the following reaction:

CH₃(PhCH₂O)CHCH₂OH+FCOCF(OCF₂CF₂

CF₃)CF₃→CH₃(PhCH₂O)CHCH₂

OCOCF(OCF₂CF₂CF₃)CF₃

→CF₃(CY^(F)CF₂O)CFCF₂

OCOCF(OCF₂CF₂CF₃)CF₃

→CF₃(CY^(F)CF₂O)CFCOF+FCOCF(OCF₂

CF₂CF₃)CF₃(IIb-30)

Further, in a case where R^(A) in the compound (IIb-1) is CH₂ClCHCl—,such a compound can be led to a compound (IIb-21) useful as aperfluoro(butenyl vinyl ether) [CF₂═CFCF₂CF₂OCF═CF₂] material by thefollowing production route:

CH₂ClCHClCH₂CH₂OCOR^(B)→CF₂

ClCFClCF₂CF₂OCOR^(B)→CF₂ClCFClCF₂

COF(IIb-21)+FCOR^(B)

Further, CF₃CF₂COOCF₂CF₂CF₃ can be led to CF₃CF₂COF (IIb-20) useful as apentafluoropropionyl fluoride material by the method of the presentinvention. The compound (IIb-20) may be added to the reaction system forthe dimerization reaction of hexafluoropropylene oxide, whereby compound(IIb-30) can be produced efficiently (JP-A-11-116529, etc).

Further, in a case where the compound (IIb) is a compound wherein R^(A)is a dioxolane skeleton, it produces a compound (IIb-30) and it can beled to a known fluorinated resin material by the following productionroute:

Explanation About Various Production Processes

In the conversion reaction of the compound (IV), the compound (VI) willbe formed together with the compound (V). The desired compound in theprocess for producing of the present invention may be the compound (V)only, the compound (VI) only, or both the compound (V) and the compound(VI).

Further, the process of the present invention can be made to be thefollowing efficient processes 1 to 3 by selecting groups in compounds.In the following, the groups not defined have the same meanings asdescribed above.

Process 1

A process wherein groups are selected so that the compound (V) and thecompound (VI) will be the same compound. By this process, the step ofseparating the product can be omitted.

For example, there may be mentioned a case where groups are selected sothat R^(AF) and R^(BF) in the compound (IVd) will be of the samestructure, and likewise a case where groups are selected so that R^(AF1)and R^(BF1) in the compound (IVd-1) will be of the same structure.Specific examples of such Process 1 will be exemplified in Process 3.

Process 2

A process wherein a group in the compound (II) is selected so that theresulting compound (VI) will be of the same structure as the compound(II). According to such a process, the resulting compound (VI) (=thecompound (II)) can be used again for the reaction with the compound (I),whereby the process of the present invention can be made to be acontinuous production process.

A specific example of Process 2 may be an example wherein a perhalogenogroup is used as R^(BF) in the compound (IIb). For example, when acompound (IIb-10) is used as the compound (IIb), the process can be madeto be the following production process.

Namely, it is a continuous process for producing a compound (Ve) whereinthe compound (Ia) and the compound (IIb-10) are reacted to form acompound (IIIc-10); the compound (IIIc-10) is fluorinated in a liquidphase to form a compound (IVd-10); then the compound (IVd-10) isconverted (preferably subjected to a thermal decomposition reaction) toobtain a compound (Ve) and a compound (IIb-10), and a part or whole ofthe compound (IIb-10) is used again for the reaction with the compound(Ia):

R^(A)CH₂OH (Ia)+FCOR^(BF10) (IIb-10)→

R^(A)CH₂OCOR^(BF10) (IIIc-10)→

R^(AF)CF₂OCOR^(BF10) (IVd-10)→

R^(AF)COF (Ve)+compound (IIb-10)

Likewise, it is a continuous process for producing a compound (Ve-1),which comprises a first step of reacting a compound (Ia-1) and acompound (IIb-1) to form a compound (IIIc-1), then reacting the compound(IIIc-1) with fluorine gas in a solvent to form a compound (IVd-1) andthen converting (preferably thermally decomposing) the compound (IVd-1)to obtain a compound (IIb-1) together with a compound (Ve-1), a secondstep of carrying out the same reactions as in the first step by usingthe compound (IIb-1) obtained by the thermal decomposition in the firststep, to obtain a compound (IIb-1) together with the compound (Ve-1),and a further step of repeating the second step by using the compound(IIb-1) obtained by the thermal decomposition in the second step:

R^(AH)CH₂OH (Ia-1)+FCOR^(BF1) (IIb-1)→

R^(AH)CH₂OCOR^(BF1) (IIIc-1)→

R^(AF1)CF₂OCOR^(BF1) (IVd-1)→

R^(AF1)COF (Ve-1)+compound (IIb-1)

Specifically, it is a continuous process wherein a compound (Ia-2) and acompound (IIb-2) are reacted to form a compound (IIIc-2); the compound(IIIc-2) is fluorinated in a liquid phase to form a compound (IVd-2);the compound (IVd-2) is converted (preferably subjected to a thermaldecomposition reaction) to obtain a compound (IIb-2) together with acompound (Ve-2); and then a part or whole of the compound (IIb-2) isused again for the reaction with the compound (Ia-2):

R¹CH₂OH (Ia-2)+FCOR² (IIb-2)→

R¹CH₂OCOR² (IIIc-2)→R³

CF₂OCOR² (IVd-2)→

R³COF (Ve-2)+compound (IIb-2)

Likewise, it is a continuous process wherein in the following productionroute employing a compound (Ia-30) and a compound (IIb-30), the formedcompound (IIb-30) is used again for the reaction with the compound(Ia-30):

(CH₃)(CH₂ClCHClCH₂CH₂O)CHCH₂

OH (Ia-30)+

FCOCF(CF₃)(OCF₂CF₂CF₃)

(IIb-30)→(CH₃)(CH₂ClCHClCH₂

CH₂O)CHCH₂OCOCF(CF₃)(OCF₂CF₂

CF₃) (IIIc-30)→(CF₃)(CF₂

ClCFClCF₂CF₂O)CFCF₂OCOCF(CF₃)(OCF₂

CF₂CF₃) (IVd-30)→(CF₃)(CF₂

ClCFClCF₂CF₂O)CFCOF (IIb-32)+compound (IIb-30)

The compound (IIb-32) can be led to a material for a fluorine resin[CF₂═CFCF₂CF₂OCF═CF₂] by a known method.

Further, in the same manner, it can be made to be a continuous processby using the formed compound (IIb-20) again for the reaction with thecompound (Ia-20) in the following production route employing thecompound (Ia-20) and the compound (IIb-20):

CH₂ClCHClCH₂CH₂OH (Ia-20)+FCOCF₂

CF₃ (IIb-20)→CH₂ClCHClCH₂CH₂

OCOCF₂CF₃ (IIIc-40)→CF₂ClCFClCF₂

CF₂OCOCF₂CF₃ (IVd-40)→FCOCF₂

CFClCF₂Cl (IIb-21)+compound (IIb-20)

Process 3

A process wherein groups are selected so that the resulting compound (V)and the compound (VI) will be of the same structure and further, theywill be of the same structure as compound (II). Such a process isparticularly preferred since it is unnecessary to separate the product,and a part or whole of the formed compound can be used again for thereaction with the compound (I).

For example, it is a process for producing a compound (Ve-2) wherein acompound (Ia-2) and a compound (Ve-2) are reacted to form a compound(IIIc-4); the compound (IIIc-4) is fluorinated in a liquid phase to forma compound (IVd-4); and then the compound (IVd-4) is converted(preferably thermally decomposed) to obtain a compound (Ve-2). And, itis a continuous process for producing the compound (Ve-2), wherein apart or whole of the formed compound (Ve-2) is used again for thereaction with the compound (Ia-2):

R¹CH₂OH (Ia-2)+FCOR³ (Ve-2)→R¹

CH₂OCOR₃ (IIIc-4)→

R³CF₂OCOR³ (IVd-4)→FCOR³

(Ve-2)

Likewise, it is a continuous process for producing a compound (IIb-31),wherein a compound (Ia-3) and a compound (IIb-31) are reacted to form acompound (IIIc-31); the compound (IIIc-31) is reacted with fluorine gasin a solvent to form a compound (IVd-41); and the compound (IVd-41) isconverted (preferably thermally decomposed). And, it is a continuousmethod for producing the compound (IIb-31), wherein a part or whole ofthe formed compound (IIb-31) is used again for the reaction with thecompound (Ia-3):

R⁴(R⁵O)CHCH₂OH (Ia-3)+

FCOCFR⁸⁰(OR⁹⁰) (IIb-31)→R⁴(R⁵O)CHCH₂OCOCFR⁸⁰

(OR⁹⁰) (IIIc-31)→

R⁸⁰(R⁹⁰O)CFCF₂OCOCFR⁸⁰

(OR⁹⁰) (IVd-41)→

compound (IIb-31)

wherein

R⁸⁰: A group corresponding to R⁴; and when R⁴ is a group containing nohydrogen atom, the same group as R⁴, and when R⁴ is a group containinghydrogen atoms, a group having all of hydrogen atoms in such a groupsubstituted by fluorine atoms;

R⁹⁰: A group corresponding to R⁵; and when R⁵ is a group containing nohydrogen atom, the same group as R⁵, and when R⁵ is a group containinghydrogen atoms, a group having all of hydrogen atoms in such a groupsubstituted by fluorine atoms.

Specifically, there is a continuous process for producing a compound(IIb-30) represented by the following production route employing acompound (Ia-31) and a compound (IIb-30):

(CH₃)(CH₃CH₂CH₂O)CHCH₂

OH (Ia-31)+FCOCF(CF₃)(OCF₂

CF₂CF₃) (IIb-30)→(CH₃)(CH₃

CH₂CH₂O)CHCH₂OCOCF( CF₃)(OCF₂

CF₂CF₃) (IIIc-310)→(CF₃)(CF₃

CF₂CF₂O)CFCF₂OCOCF(CF₃)(OCF₂

CF₂CF₃) (IVd-410)→FCOCF(CF₃)(OCF₂

CF₂CF₃) (IIb-30)

In the above process, the compound (IIIc-310) and the compound (IVd-410)are novel compounds. From the compounds, the compound (IIb-30)) can beobtained. The compound (IIb-30) can be led to perfluoro(propylvinylether) which is a fluorinated resin material, by a known method.Further, there is a continuous process for producing a compound (IIb-20)represented by the following production route when a compound (Ia-21)and a compound (IIb-20) are employed:

CH₃CH₂CH₂OH

(Ia-21)+FCOCF₂CF₃ (IIb-20)→

CH₃CH₂CH₂OCOCF₂CF₃ (IIIc-41)→

CF₃CF₂CF₂OCOCF₂CF₃ (IVd-41)→

compound (IIb-20)

Likewise, specifically, there is a continuous process for producing acompound (IIb-21) represented by the following production routeemploying a compound (Ia-20) and a compound (IIb-21):

CH₂ClCHClCH₂CH₂OH (Ia-20)+FCOCF₂

CFClCF₂Cl (IIb-21)→

CH₂ClCHClCH₂CH₂OCOCF₂

CFClCF₂Cl (IIIc-42)→

CF₂ClCFClCF₂CF₂OCOCF₂

CFClCF₂Cl (IVd-42)→

compound (IIb-21)

According to the process of the present invention, it is possible toproduce various fluorine-containing compounds by using the compound (I)and the compound (II) which are inexpensively available materials. Withrespect to the compound (I) and the compound (II), various compoundswhich are different in the structure of R^(A) or the structure of R^(B),are commercialized and inexpensively available. And, according to theprocess of the present invention, from such starting material compounds,a fluorine-containing compound such as an acid fluoride compound can beproduced by a short process in good yield. Further, by using the processof the present invention, a low molecular fluorine-containing compoundwhich used to be difficult to obtain by a conventional process, or afluorine-containing compound having a complex structure, can easily besynthesized. Further, the process of the present invention is a processexcellent in wide applicability, which can be applied to variouscompounds without being limited to the compounds described above asspecific examples. Accordingly, a fluorine-containing compound having adesired skeleton can freely be produced. Further, by selecting thestructures of R^(A) and R^(B), the process of the present invention canbe made to be a continuous process.

Further, according to the present invention, a novel acid fluoridecompound or its intermediate can be provided which can be used as afluorinated resin material.

In the foregoing description, the reaction conditions (such as theamounts of the respective compounds to be reacted, the temperatures, thepressures, etc.), etc. in the process of the present invention werespecifically described with respect to the compound (Ia), the compound(IIb), the compound (IIIc), the compound (IVd) and the compound (Ve).However, the above-described reaction conditions can be applicable alsoin cases wherein various compounds included in such compounds, and thecompounds (I) to (IV) are employed. Specifically, for example, in thecase of the compound (Ia), a compound (Ia-1), a compound (Ia-2) or acompound (Ia-3) may, for example, be mentioned; in the case of thecompound (IIb), a compound (IIb-1), a compound (IIb-2) or a compound(IIb-3) may, for example, be mentioned; in the case of the compound(IIIc), a compound (IIIc-1), a compound (IIIc-2) or a compound (IIIc-3)may, for example, be mentioned; in the case of a compound (IVd), acompound (IVd-1), a compound (IVd-2) or a compound (IVd-3) may, forexample, be mentioned; and in the case of the compound (Ve), a compound(Ve-1), a compound (Ve-2) or a compound (Ve-3) may, for example, bementioned.

EXAMPLES

In the following, the present invention will be described in detail withreference to Examples, but the present invention is not limited thereto.Further, in the following, gas chromatography is referred to as GC, andgas chromatography mass spectrometry is referred to as GC-MS. Further,the purity determined from the peak area ratio of GC is referred to asGC purity, and the yield is referred to as GC yield. The yielddetermined from the peak area ratio of the NMR spectrum will be referredto as NMR yield. Further, tetramethylsilane will be represented by TMS,and CCl₂FCClF₂ will be represented by R-113. Further, the NMR spectrumdata are shown as an apparent chemical shift range. The standard valueof the standard material CDCl₃ in ¹³C-NMR was set to be 76.9 ppm. In thequantitative analysis by ¹⁹F-NMR, C₆F₆ was employed as the internalstandard.

Example 1 Production of CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂CH₂CH₃)CH₃

CH₃(CH₃CH₂CH₂O)CHCH₂OH (16.5 g) was put into a flask and stirred whilebubbling nitrogen gas. CF₃(CF₃CF₂CF₂O)CFCOF (46.5 g) was added dropwisethereto over a period of 2 hours while maintaining the internaltemperature at from 26 to 31° C. After completion of the dropwiseaddition, stirring was continued at room temperature for 2 hours, and 50ml of a saturated sodium hydrogen carbonate aqueous solution was addedat an internal temperature of not higher than 15° C. 50 ml of water and135 ml of chloroform were added thereto, followed by liquid separationto obtain a chloroform layer as an organic layer. Further, the organiclayer was washed with 50 ml of water, dried over magnesium sulfate andthen subjected to filtration to obtain a crude liquid.

The crude liquid was concentrated by an evaporator, followed bydistillation under reduced pressure to obtain a fraction (1) of from 23to 52° C./4.0 kPa (29 g), a fraction (2) of from 52 to 61° C./from 3.6to 4.0 kPa (19 g) and a fraction (3) of from 52 to 70° C./from 1.3 to3.6 kPa (4 g). The GC purity was 68% with the fraction (1), 98% with thefraction (2) and 97% with the fraction (3). The NMR spectrum of thefraction (2) was measured to confirm that the main component was amixture of diastereomers of CF₃CF(OCF₂CF₂CF₃)COOCH₂CH(OCH₂CH₂CH₃)CH₃.NMR spectrum of the fraction (2).

¹H-NMR(399.8 MHz,solvent CDCl₃,standard: TMS) δ (ppm):0.90(t,J=7.5Hz,3H),1.20(d,J=5.4Hz,3H),1.50-1.60(m,2H),3.33-3.50(m,2H),3.64-3.74(m,1H),4.23-4.29(m,1H),4.34-4.41(m,1H).

¹⁹F-NMR(376.2 MHz,solvent CDCl₃,standard: CFCl₃)δ(ppm):−80.9(1F),−82.3(3F),−83.1(3F),−87.4(1F),−130.7(2F),−132.7(1F).

Further, by GC, it was confirmed that the main component contained inthe fraction (1) and the fraction (3) wasCF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂CH₂CH₃)CH₃.

Example 2 Production of CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCF₂CF₂CF₃)CF₃ by aFluorination Reaction

The fraction (2) and the fraction (3) obtained in Example 1 were mixed,and 19.5 g thereof was dissolved in R-113 (250 g) to obtain a fractionsolution. On the other hand, into a 500 ml autoclave made of nickel, NaF(26.1 g) was introduced, and R-113 (324 g) was added thereto, followedby stirring and cooling to −10° C. Nitrogen gas was blown thereinto for1 hour, and then fluorine gas diluted to 20% with nitrogen gas, wasblown thereinto for 1 hour at a flow rate of 5.66 l/hr. While blowing itat the same flow rate, the above-mentioned fraction solution wasinjected over a period of 19.4 hours.

Then, while blowing the fluorine gas diluted to 20% with nitrogen gas atthe above-mentioned flow rate, a R-113 solution of benzene (0.01 g/ml)was injected, and the outlet valve of the autoclave was closed, and whenthe pressure became 0.12 MPa, the inlet valve of the autoclave wasclosed, whereupon stirring was continued for 1 hour.

Further, such operation was repeated four times during a period wherethe temperature was raised from −10° C. to room temperature andthereafter five times at room temperature. During this period, benzenewas injected in a total amount of 0.291 g and R-113 was injected in atotal amount of 45.0 g. Thereafter, nitrogen gas was blown thereinto for2 hours, and the reaction mixture was taken out by decantation. Theobtained crude liquid was concentrated by an evaporator, and the productwas quantitatively analyzed by ¹⁹F-NMR, whereby the yield was 69%. Apart of the crude liquid was taken and distilled under reduced pressureto obtain purified CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCF₂CF₂CF₃)CF₃. The productwas a mixture of diastereomers.

Boiling point: 46 to 51° C./5.2 kPa.

High resolution mass spectrum (CI method) 664.9496 (M+H. theoreticalvalue: C₁₂HF₂₄O₄=664.9492).

¹⁹F-NMR(564.6 MHz,solvent CDCl₃/C₆F₆,standard:CFCl₃)δ(ppm):−80.6(1F),−80.8 and−80.9(3F),−81.6˜−83.1(2F),−82.6(6F),−82.8(3F),−86.7(1F),−87.4(1F),−87.5(1F),−130.6(4F),−132.2(1F),−145.7and −145.9(1F).

¹³C-NMR(150.8 MHz,solvent CDCl₃/C₆F₆,standard:CDCl₃) δ(ppm) :100.26 and100.28,102.8,106.8,107.0,116.0,116.2,116.5 and116.6,117.4,117.5,117.9,117.9,152.2 and 152.3.

Example 3 Production of CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCF₂CF₂CF₃)CF₃ by aFluorination Reaction

The operation was carried out in the same manner as in Example 2 exceptthat as the solvent, perfluorotributylamine was used instead of R-113,to obtain CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCF₂CF₂CF₃)CF₃. The NMR yield was70%.

Example 4 Production of CF₃CF₂COOCH₂CH₂CH₃

CH₃CH₂CH₂OH (268.6 g) was put into a flask and stirred while bubblingnitrogen gas. CF₃CF₂COF (743 g) was fed over a period of 3.75 hourswhile maintaining the internal temperature at from 20 to 25° C. Aftercompletion of the feeding, stirring was continued for 1.25 hours at roomtemperature, and 2 l of a saturated sodium hydrogencarbonate aqueoussolution was added at an internal temperature of not higher than 20° C.Liquid separation was carried out, and the organic layer was washed with1 l of water, to obtain a crude liquid (775 g). Then, distillation underreduced pressure was carried out to obtain a fraction (556 g).

Boiling point: 50° C./18.6 kPa.

NMR spectrum of the fraction

¹H-NMR(399.8 MHz,solvent CDCl₃,standard:TMS) δ(ppm):0.98(q,J=7.3Hz,3H),1.76(m,2H),4.34(t,J=6.7 Hz,2H).

¹⁹F-NMR(376.2 MHz,solvent CDCl₃,standard:CFCl₃)δ(ppm):−84.0(3F),−122.6(2F).

Example 5 Production of CF₃CF₂COOCF₂CF₂CF₃

12 g of the fraction obtained in Example 4 was dissolved in R-113 (250g) to obtain a fraction solution. On the other hand, into a 500 mlautoclave made of nickel, R-113 (312 g) was added, followed by stirringand cooling to −10° C. Nitrogen was blown thereinto for 1 hour, and thenfluorine gas diluted to 20% with nitrogen gas, was blown thereinto for 1hour at a flow rate of 5.66 l/hr, and while blowing it at the same flowrate, the fraction solution was injected over a period of 14.75 hours.

Then, while blowing the fluorine gas diluted to 20% with nitrogen gas atthe above-described flow rate, a R-113 solution of benzene (0.01 g/ml)was injected, whereupon the outlet valve of the autoclave was closed.When the pressure became 0.12 MPa, the inlet valve of the autoclave wasclosed, and stirring was continued for 1 hour.

Further, such an operation was repeated three times during a periodwhere the temperature was raised from −10° C. to room temperature andthereafter six times at room temperature. During this period, benzenewas injected in a total amount of 0.323 g, and R-113 was injected in atotal amount of 50 g. Thereafter, nitrogen gas was blown thereinto for 2hours. The product was quantitatively analyzed by ¹⁹F-NMR, whereby theyield was 77%.

¹⁹F-NMR(376.2 MHz,solvent CDCl₃,standard:CFCl₃) δ(ppm):−82.5(t,J=7.0Hz,3F),−83.9(s,3F),−88.6(q,J=7.0 Hz,2F),−122.8(s,2F),−130.9(s,2F).

Example 6 Production of CF₃CF(OCF₂CF₂CF₃)COF by a Liquid Phase ThermalDecomposition

CF₃CF(OCF₂CF₂CF₃)COOCF₂CF(OCF₂CF₂CF₃)CF₃ (15 g) obtained in Example 2,was charged into a 100 ml ample made of stainless steel and left tostand in an oven maintained at 200° C. Two hours later, it was taken outand cooled to room temperature, whereupon a liquid sample (14.5 g) wasrecovered. By GC-MS, it was confirmed that CF₃CF(OCF₂CF₂CF₃)COF was themain product. The NMR yield was 85%.

Example 7 Production of CF₃CF(OCF₂CF₂CF₃)COF by a Gas Phase ThermalDecomposition of CF₃CF(OCF₂CF₂CF₃)COOCF₂CF(OCF₂CF₂CF₃)CF₃

An empty U-shaped reactor made of Inconel 600 (internal capacity: 200ml) was immersed in a salt bath furnace maintained at 250° C. 1 l/hr ofnitrogen and CF₃CF(OCF₂CF₂CF₃)COOCF₂CF(OCF₂CF₂CF₃)CF₃ obtained inExample 2 were supplied at a flow rate of 15 g/hr from an inlet of thereactor. The retention time was maintained from 10 to 12 seconds. On theoutlet side of the reactor, a dry ice/methanol and liquid nitrogen trapswere attached to recover the reaction crude gas. After the reaction for2 hours, a liquid sample (23 g) was recovered from the traps. By GC-MS,it was confirmed that CF₃CF(OCF₂CF₂CF₃)COF was the main product. The NMRyield was 73%.

Example 8 Production of CF₃CF₂COF by a Liquid Phase ThermalDecomposition

CF₃CF₂COOCF₂CF₂CF₃ (20 g) obtained in Example 5 andchlorotrifluoroethylene oligomer (120 g) were charged into a 200 mlautoclave made of nickel and equipped with a reflux condenser and heatedto 200° C. The reflux condenser was cooled by circulating cooling water,and when the pressure became at least 0.1 MPa, the gas was purged whilemaintaining the pressure to recover a gaseous sample (15 g). By GC-MS,it was confirmed that CF₃CF₂COF was the main product. The GC yield was90%.

Example 9 Production of CF₃CF₂COOCH₂CH₂CHClCH₂Cl

CH₂ClCHClCH₂CH₂OH (30 g) was put into a flask and stirred while bubblingnitrogen gas. CF₃CF₂COF (310 g) was fed over a period of 3 hours whilemaintaining the internal temperature at from 25° C. to 30° C. Aftercompletion of the feeding, 50 ml of a saturated sodium hydrogencarbonateaqueous solution was added at an internal temperature of not higher than15° C. 50 ml of chloroform was added thereto, followed by liquidseparation to obtain a chloroform layer as an organic layer. Further,the organic layer was washed twice with 200 ml of water, dried overmagnesium sulfate and then subjected to filtration to obtain a crudeliquid. The crude liquid was concentrated by an evaporator, and thendistilled under reduced pressure to obtain a fraction of from 73 to 75°C./0.9 kPa (24 g). This fraction was purified by silica gel columnchromatography (the developing solvent was hexane:ethyl acetate=20:1) toobtain a purified product (18.8 g). The GC purity was 98%. From the NMRspectrum, it was confirmed that the above-identified compound was themain component.

¹H-NMR(399.8 MHz,solvent CDCl₃, standard:TMS)δ(ppm):2.11(m,1H),2.52(m,1H),3.69(dd,J=7.9,11.4Hz,1H),3.84(dd,J=4.7,11.4 Hz,1H),4.15(m,1H),4.60(m,2H).

¹⁹F-NMR(376.2 MHz,solvent CDCl₃,standard:CFCl₃)δ(ppm):−83.8(3F),−122.5(2F).

Example 10 Production of CF₃CF₂COOCF₂CF₂CFClCF₂Cl by a FluorinationReaction

Into a 500 ml autoclave made of nickel, R-113 (201 g) was added,followed by stirring and cooling to −10° C. Nitrogen gas was blownthereinto for 1 hour, and then fluorine gas diluted to 20% with nitrogengas, was blown thereinto for 1 hour at a flow rate of 5.66 l/hr. Whileblowing the fluorine gas at the same flow rate, a solution havingCF₃CF₂COOCH₂CH₂CHClCH₂Cl (6.58 g) obtained in Example 9 dissolved inR-113 (134 g), was injected over a period of 6.9 hours.

Then, while blowing the fluorine gas at the same flow rate, a R-113solution of benzene (0.01 g/ml) was injected, whereupon the outlet valveof the autoclave was closed. When the pressure became 0.12 MPa, theinlet valve of the autoclave was closed, and stirring was continued for1 hour. Further, the same operation of injecting benzene was repeatedonce while raising the temperature from −10° C. to 40° C. and then eighttimes at 40° C. The total amount of benzene injected was 0.330 g, andthe total amount of R-113 injected was 33 ml. Further, nitrogen gas wasblown thereinto for 2 hours. The product was quantitatively analyzed by¹⁹F-NMR, whereby the yield of the above-identified compound was 51%.

¹⁹F-NMR(376.2 MHz,solvent CDCl₃ standard:CFCl₃)δ(ppm):−65.4(2F),−84.2(3F),−85.4(2F),−119.1(2F),−123.1(2F),−132.5(1F).

Example 11 Production of a Mixture of CF₂ClCFClCF₂COOCH₂CH₂CHClCH₂Cl andCF₂ClCF₂CFClCOOCH₂CH₂CHClCH₂Cl

CH₂ClCHClCH₂CH₂OH (49.5 g) was put into a flask and stirred whilebubbling nitrogen gas. A mixture (86.1 g) of CF₂ClCFClCF₂COF andCF₂ClCF₂CFClCOF in 89:11 (molar ratio) was added dropwise over a periodof 1 hour and 40 minutes while maintaining the internal temperature atfrom 25 to 30° C. After completion of the dropwise addition, stirringwas continued at room temperature for 2 hours and 45 minutes, and asaturated sodium hydrogencarbonate aqueous solution (100 ml) was addedthereto while keeping the internal temperature not to exceed 15° C. 150ml of chloroform was added thereto, followed by liquid separation toobtain a chloroform layer. Further, the chloroform layer was washedtwice with 200 ml of water, dried over magnesium sulfate and thensubjected to filtration to obtain a crude liquid. The crude liquid wasconcentrated by an evaporator and then distilled under reduced pressureto obtain a fraction (1) of from 99 to 106° C./0.48 kPa (55.4 g), afraction (2) of from 100 to 109° C./0.47 kPa (7.9 g). The GC purity asthe above mixture was 85% with the fraction (1) and 84% with thefraction (2).

The fraction (1) (9.4 g) was purified by silica gel columnchromatography (the developing solvent was hexane:ethyl acetate=20:1) toobtain a purified product (7.5 g). The GC purity of the purified productwas 98%. From the NMR spectrum of the purified product, it was confirmedthat a mixture of CF₂ClCFClCF₂COOCH₂CH₂CHClCH₂Cl andCF₂ClCF₂CFClCOOCH₂CH₂CHClCH₂Cl was the main component, and their ratiowas 87:13 (molar ratio).

CF₂ClCFClCF₂COOCH₂CH₂CHClCH₂Cl:

¹H-NMR(399.8 MHz,solvent CDCl₃,standard:TMS)δ(ppm):2.09(m,1H),2.52(m,1H),3.69(dd,J=7.6,11.4Hz,1H),3.84(dd,J=4.7,11.4 Hz,1H),4.17(m,1H),4.58(m,2H).

¹⁹F-NMR(376.2 MHz,solvent CDCl₃,standard:CFCl₃)δ(ppm):−63.6(1F),−64.8(1F),−110.9(1F),−114.0(1F),−131(1F).

CF₂ClCF₂CFClCOOCH₂CH₂CHClCH₂Cl:

¹H-NMR(399.8 MHz,solvent CDCl₃,standard:TMS)δ(ppm):2.09(m,1H),2.52(m,1H),3.69(dd,J=7.6,11.4Hz,1H),3.84(dd,J=4.7,11.4 Hz,1H),4.17(m,1H),4.58(m,2H).

¹⁹F-NMR(376.2 MHz,solvent CDCl₃,standard:CFCl₃)δ(ppm):−66.9(1F),−67.0(1F),−113.4(1F),−117.6(1F),−129.0(1F).

Example 12 Production of a Mixture of CF₂ClCFClCF₂COOCF₂CF₂CFClCF₂Cl andCF₂ClCF₂CFClCOOCF₂CF₂CFClCF₂Cl by a Fluorination Reaction

Into a 500 ml autoclave made of nickel, R-113 (200 g) was added andstirred, and nitrogen gas was blown thereinto at room temperature for 1hour. Then, fluorine gas diluted to 20% with nitrogen gas, was blownthereinto for 1 hour at a room temperature at a flow rate of 5.66 l/hr.

Then, while blowing the fluorine gas at the same flow rate, a solutionhaving a mixture (12 g) of CF₂ClCFClCF₂COOCH₂CH₂CHClCH₂Cl andCF₂ClCF₂CFClCOOCH₂CH₂CHClCH₂Cl obtained in Example 1 in 87:13 (molarratio) dissolved in R-113 (243 g), was injected over a period of 11.5hours.

Then, while blowing the fluorine gas at the same flow rate, a R-113solution of benzene (0.01 g/ml) was injected, whereupon the outlet valveof the autoclave was closed. When the pressure became 0.12 MPa, theinlet valve of the autoclave was closed, and stirring was continued for1 hour. Further, the same operation of injecting benzene was repeatedonce while raising the temperature from room temperature to 40° C. andthen eight times at 40° C. The total amount of benzene injected was0.342 g, and the total amount of R-113 injected was 33 ml. Further,nitrogen gas was blown thereinto for 2 hours. The yield of theabove-identified mixture obtained from the ¹⁹F-NMR spectrum (internalstandard: C₆F₆) of the product was 80%.

CF₂ClCFClCF₂COOCF₂CF₂CFClCF₂Cl:

¹⁹F-NMR(564.6 MHz,solvent CDCl₃,standard:CFCl₃)δ(ppm):−64.4˜−65.9(2F),−65.4(2F),−85.5˜−86.3(2F),−111.1˜−115.1(2F),−118.7˜−120.1(2F),−132.0(1F),−132.5(1F).

¹³C-NMR(150.8 MHz,solvent CDCl₃,standard:CDCl₃)δ(ppm):104.4,104.5,109.4,110.8,116.6,124.3,124.6,152.0.

CF₂ClCF₂CFClCOOCF₂CF₂CFClCF₂Cl:

¹⁹F-NMR(564.6 MHz,solvent CDCl₃,standard:CFCl₃) δ(ppm):−64.4˜−66.0(2F),−68.0(2F),−85.5˜−86.3(2F),−113.7˜−115.3(2F),−118.7˜−120.1(2F),−130.0(1F),−132.5(1F).

¹³C-NMR (150.8 MHz,solvent CDCl₃,standard:CDCl₃)δ(ppm):99.0,104.4,110.2,110.8,116.6,122.8,124.6,153.2.

Example 13 Production of CH₃CHClCOOCH₂Cy

Into a 200 ml three-necked flask, 2-chloropropionic acid (28.5 g),cyclohexane methanol (30.0 g), sulfuric acid (5 ml) and toluene (75 ml)were charged and stirred. The mixture was heated until the internaltemperature became 117° C. and then left to cool.

The reaction mixture was added to a saturated sodium carbonate aqueoussolution (170 ml), whereupon the liquid separated into 2 layers wereseparated. From the aqueous layer, an organic substance was extractedwith toluene (100 ml) and put together with the organic layer, followedby drying over sodium carbonate. After the filtration, toluene wasdistilled off to obtain a crude product (52.4 g). This product wasdistilled under reduced pressure to obtain CH₃CHClCOOCH₂Cy (45.9 g) as afraction having a GC purity of at least 94%.

Boiling point: 140 to 142° C./4.5 to 4.7 kPa

¹H-NMR(300.40 MHz,solvent:CDCl₃,standard:TMS)δ(ppm):0.90˜1.03(m,2H),1.07˜1.32(m,3H),1.60˜1.72(m,6H),1.68(d,J=6.9Hz,3H),3.97(dd,J=2.7,6.3 Hz,2H),4.38(q,J=6.9 Hz,1H).

Example 14 Production of CH₃CH(OCH₂Cy)COOCH₂Cy

Into a 300 ml four-necked flask, N,N-dimethylformamide (70 ml) andsodium hydride (60%, 9.77 g) were charged and stirred, and HOCH₂Cy (25.1g) was added dropwise under cooling with ice. After completion of thedropwise addition, stirring was continued at room temperature for 1hour. Then, CH₃CHClCOOCH₂Cy (45.0 g) obtained in Example 13 was addeddropwise over a period of 100 minutes while suitably cooling so that theinternal temperature was maintained at a level of not higher than 40° C.After completion of the dropwise addition, stirring was continued for 3hours at a bath temperature of 88° C. After cooling, 2 mol/lhydrochloric acid (50 ml) was added dropwise over a period of 8 minutesunder cooling with ice, and then the mixture was added to 2 mol/lhydrochloric acid (150 ml). It was extracted with a mixture (400 ml) ofhexane:ethyl acetate=2:1, and the organic layer was washed twice withwater (100 ml). The organic layer was dried over magnesium sulfate, andthe solvent was distilled off to obtain a residue (64.0 g). This residuewas distilled under reduced pressure to obtain CH₃CH(OCH₂Cy)COOCH₂Cy(44.4 g) having a GC purity of 96.8%.

Boiling point: 120 to 138° C./0.70 to 0.80 kPa.

¹H-NMR(300.40 MHz,solvent:CDCl₃,standard:TMS)δ(ppm):0.77˜1.03(m,4H),1.03˜1.31(m,6H),1.36(d,J=4.8Hz,3H),1.47˜1.82(m,12H),3.11(dd,J=6.6,9.0 Hz,1H),3.33(dd,J=6.6,9.0Hz,1H),3.82˜3.99(m,3H).

Example 15 Production of CH₃CH(OCH₂Cy)CH₂OH

In a nitrogen stream, into a 500 ml four-necked flask, toluene (150 ml)and bis(2-methoxyethoxy)aluminum sodium hydride (65% toluene solution,175.1 g) were charged and stirred, and CH₃CH(OCH₂Cy)COOCH₂Cy (30.0 g)obtained in Example 14 was added dropwise over a period of 70 minutes atan internal temperature of not higher than 45° C. Stirring was continuedfor 1.5 hours at an internal temperature of 85° C., followed by coolingin an ice bath to an internal temperature of 2.2° C., whereupon 26 ml of2 mol/l hydrochloric acid was added dropwise thereto.

The reaction mixture was added to 1500 ml of 2 mol/l hydrochloric acid,and extracted with t-butylmethyl ether (700 ml). From the aqueous layersubjected to liquid separation, an organic substance was furtherextracted with t-butylmethyl ether (200 ml) and put together with theorganic layer, followed by washing with water (150 ml). The organiclayer was dried over magnesium sulfate and subjected to filtration, andthe solvent was distilled off to obtain a crude product (29.3 g). Thiscrude product was distilled under reduced pressure to obtainCH₃CH(OCH₂Cy)CH₂OH (14.6 g) having a GC purity of 98.9 g.

Boiling point: 112 to 128° C./3.2 to 3.3 kPa.

¹H-NMR(300.40 MHz,solvent:CDCl₃,standard:TMS)δ(ppm):0.85˜1.03(m,2H),1.10(d,J=6.0Hz,3H),1.12˜1.34(m,3H),1.48˜1.82(m,6H),2.08(dd,J=3.9,8.1Hz,1H),3.17(dd,J=6.8,9.0 Hz,1H),3.33˜3.62(m,4H).

Example 16 Production of CH₃CH(OCH₂Cy)CH₂OCOCF(CF₃)OCF₂CF₂CF₃

CH₃CH(OCH₂Cy)CH₂OH (13.8 g) having a GC purity of 98% obtained inExample 15, was put into a flask and stirred while bubbling nitrogengas. FCOCF(CF₃)OCF₂CF₂CF₃ (32 g) was added dropwise over a period of 30minutes while maintaining the internal temperature at from 25 to 30° C.After completion of the dropwise addition, stirring was continued atroom temperature for 3 hours, and 50 ml of a saturated sodiumhydrogencarbonate aqueous solution was added at an internal temperatureof not higher than 15° C.

The obtained crude liquid was subjected to liquid separation, and thelower layer was washed twice with 50 ml of water, dried over magnesiumsulfate and then subjected to filtration to obtain a crude liquid. Thecrude liquid was purified by silica gel column chromatography(developing solvent: dichloropentafluoropropane (tradename: AK-225)), toobtain CH₃CH (OCH₂Cy)CH₂OCOCF(CF₃)OCF₂CF₂CF₃ (15.4 g). The GC purity was99%.

¹H-NMR(399.8 MHz,solvent:CDCl₃,standard:TMS)δ(ppm):0.82˜0.95(m,2H),1.07˜1.28(m,3H),1.17,1.17(d,J=6.4 Hz,d,J=6.4Hz,3H),1.44˜1.55(m,1H),1.61˜1.75(m,5H),3.20,3.28(dd,J=6.8,8.8Hz,ddd,J=3.2,6.4,8.8 Hz,2H),3.60˜3.68(m,1H),4.21˜4.26,4.32˜4.40(m,2H).

¹⁹F-NMR(376.2 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):−80.4(1F),−81.8(3F),−82.5(3F),−86.8(1F),−130.2(2F),−132.1(1F).

Example 17 Production of Cy^(F)CF₂OCF(CF₃)CF₂OCOCF(CF₃)OCF₂CF₂CF₃

Into a 500 ml autoclave made of nickel, R-113 (312 g) was added, stirredand maintained at 25° C. At the gas outlet of the autoclave, a condensermaintained at 20° C, a NaF pellet packed layer and a condensermaintained at −10° C. were installed in series. Further, a liquidreturning line was installed to return the condensed liquid from thecondenser maintained at −10° C. to the autoclave. Nitrogen gas was blownthereinto for 1 hour, and then fluorine gas diluted to 20% with nitrogengas, was blown thereinto for 1 hour at a flow rate of 8.63 l/hr. Then,while blowing the fluorine gas at the same flow rate, a solution havingCyCH₂OCH(CH₃)CH₂OCOCF(CF₃)OCF₂CF₂CF₃ (4.98 g) obtained in Example 16dissolved in R-113 (100 g), was injected over a period of 7.8 hours.

Then, while blowing the fluorine gas at the same flow rate, the internalpressure of the autoclave was raised to 0.15 MPa, and a R-113 solutionhaving a benzene concentration of 0.01 g/ml, was injected in an amountof 6 ml while raising the temperature from 25° C. to 40° C., whereuponthe benzene injection inlet of the autoclave was closed, and stirringwas continued for 0.3 hour.

Then, while maintaining the internal pressure of the reactor at 0.15 MPaand the internal temperature of the reactor at 40° C., 3 ml of theabove-mentioned benzene solution was injected, whereupon the benzeneinjection inlet of the autoclave was closed, and stirring was continuedfor 0.3 hour. Further, the same operation was repeated three times. Thetotal amount of benzene injected was 0.184 g, the total amount of R-113injected was 18 ml. Further, while blowing the fluorine gas at the sameflow rate, stirring was continued for 0.8 hour.

Then, the internal pressure of the reactor was adjusted to beatmospheric pressure, and nitrogen gas was blown thereinto for 1.5hours. The desired product was quantitatively analyzed by ¹⁹F-NMR,whereby the yield of the above-identified compound was 75%.

¹⁹F-NMR(376.0 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):−68.1˜70.4(2F),−80.4˜−81.1(4F),−82.4(3F),−82.7(3F),−87.0(1F),−87.4(2F),−119.5˜−143.5(10F),−130.6(2F),−132.7(1F),−146.0and −146.3(1F),−187.9(1F).

Example 18 Production of Cy^(F)CF₂OCF(CF3)COF

Cy^(F)CF₂OCF(CF₃)CF₂OCOCF(CF₃)OCF₂CF₂CF₃ (0.9 g) obtained in Example 17,was charged into a flask together with a NaF powder (0.01 g) and heatedat 120° C. for 5.5 hours and at 140° C. for 5 hours in an oil bath withvigorous stirring. At an upper portion of the flask, a reflux condenseradjusted at a temperature of 20° C., was installed. After cooling, theliquid sample (0.9 g) was recovered. By GC-MS, it was confirmed thatCF₃CF(OCF₂CF₂CF₃)COF and the above-identified compound were the mainproducts. The NMR yield was 66.0%.

¹⁹F-NMR (376.0 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):25.8(1F),−67.4(1F),−75.6(1F),−82.4(3F),−119.5˜−143.5(10F),−132.4(1F),−187.9(1F).

Example 19 Production of CH₃CHClCOO(CH₂)₉CH₃

Into a 500 ml four-necked flask, triethylamine (68.4 g) and 1-decanol(51.0 g) were charged and stirred, and while maintaining the internaltemperature at a level of not higher than 12° C., 2-chloropropionylchloride (42.9 g) was added dropwise over a period of 75 minutes undercooling with ice. The mixture was diluted with dichloromethane (50 ml)and stirred for 30 minutes. The reaction mixture was added to water (400ml) for liquid separation into two layers. An organic substance wasextracted from the aqueous layer with dichloromethane (100 ml) and puttogether with the organic layer. The above operation was carried out inone more batch in a scale of 1-decanol (8.4 g), and the organic layersof the two batches were put together and washed with water (400 ml, 300ml) and dichloromethane (100 ml) was added thereto, followed by liquidseparation.

The organic layer was dried over magnesium sulfate and filtered, andthen the solvent was distilled off to obtain a residue (86.6 g). Thisresidue was distilled under reduced pressure to obtainCH₃CHClCOO(CH₂)₉CH₃ (64.8 g) having a GC purity of 89.9%.

Boiling point: 135 to 139° C./0.63 to 0.67 kPa

¹H-NMR(300.40 MHz,solvent:CDCl₃,standard:TMS) δ(ppm):0.88(t,J=6.9Hz,3H),1.3˜1.5(m,14H),1.6˜1.7(m,2H),1.77(d,J=6.9Hz,3H),4.1˜4.2(m,2H),4.39(q,J=6.9 Hz,1H).

Example 20 Production of CH₃CH(O(CH₂)₉CH₃)COO(CH₂)₉CH₃

Into a 500 ml eggplant type flask, 1-decanol (180 g) and a methanolsolution of sodium methylate (28%) were charged, stirred and heatedunder reduced pressure to distill off methanol. By GC, it was confirmedthat no methanol remained in the reaction solution. Into a 1 lfour-necked flask, N,N-dimethylformamide (150 ml) andCH₃CHClCOO(CH₂)₉CH₃ (27.1 g) obtained in Example 19 were charged andstirred, and a solution of sodium decylate obtained in the aboveoperation was added dropwise at an internal temperature of not higherthan 25° C. The mixture was heated to an internal temperature of 70° C.and stirred for 30 minutes.

This was carried out in two batches, and the reaction crude liquids puttogether were washed three times with water (200 ml). An organicsubstance was extracted from the aqueous layer with a mixed liquid (450ml) of hexane:ethyl acetate=2:1 and put together with the organic layer,and the solvent and 1-decanol were distilled off from the organic layerto obtain CH₃CH(O(CH₂)₉CH₃)COO(CH₂)₉CH₃ (70.8 g) having a GC purity of90.0%.

¹H-NMR(300.40 MHz,solvent:CDCl₃,standard:TMS) δ(ppm):0.88(t,J=7.2Hz,6H),1.2˜1.5(m,28H),1.44(d,J=7.5Hz,3H),1.5˜1.7(m,4H),3.3˜3.4(m,1H),3.5˜3.6(m,1H),3.93(q,J=6.9Hz,1H),4.0˜4.2(m,2H).

Example 21 Production of CH₃CH(O(CH₂)₉CH₃)CH₂OH

In a nitrogen stream, into a 1 l four-necked flask, toluene (300 ml) andbis(2-methoxyethoxy)aluminum sodium hydride (65% toluene solution, 214g) were charged and stirred, and CH₃CH(O(CH₂)₉CH₃)COO(CH₂)₉CH₃ (30.0 g)obtained in Example 20 was added dropwise over a period of 45 minutes atan internal temperature of not higher than 20° C. The mixture wasstirred for 1.5 hours at an internal temperature of 90° C. and thencooled in an ice bath, whereupon 20 ml of 2 mol/l hydrochloric acid wasadded dropwise.

The reaction mixture was added to 1000 ml of 2 mol/l hydrochloric acidand extracted with t-butylmethyl ether (800 ml). From the aqueous layersubjected to liquid separation, an organic substance was extracted witht-butylmethyl ether (400 ml) and put together with the organic layer.

The organic layer was dried over magnesium sulfate and subjected tofiltration, and then, the solvent was distilled off to obtain a crudeproduct (63.4 g). Under reduced pressure and heating, the solvent and1-decanol were distilled off to obtain CH₃CH(O(CH₂)₉CH₃)CH₂OH (16.0 g)having a GC purity of 97%.

¹H-NMR(300.40 MHz,solvent:CDCl₃,standard:TMS) δ(ppm):0.88(t,J=6.9Hz,3H),1.09(d,J=6.3Hz,3H),1.2˜1.4(m,14H),1.5˜1.7(m,2H),2.1(bs,1H),3.3˜3.6(m,5H).

Example 22 Production of CH₃CH(O(CH₂)₉CH₃)CH₂OCOCF(CF₃)OCF₂CF₂CF₃

CH₃CH(O(CH₂)₉CH₃)CH₂OH (15.5 g) having a GC purity of 97% obtained inExample 21 and triethylamine (15.2 g) were put into a flask and stirredin an ice bath. FCOCF(CF₃)OCF₂CF₂CF₃ (32 g) was added dropwise over aperiod of 30 minutes while maintaining the internal temperature at alevel of not higher than 100C. After completion of the dropwiseaddition, the mixture was adjusted to room temperature, stirred for 2hours and then added to 100 ml of ice water.

The obtained crude liquid was subjected to liquid separation, and thelower layer was washed twice with 100 ml of water, dried over magnesiumsulfate and then subjected to filtration to obtain a crude liquid. Thecrude liquid was purified by silica gel column chromatography(developing solvent: AK-225) to obtainCH₃CH(O(CH₂)₉CH₃)CH₂OCOCF(CF₃)OCF₂CF₂CF₃ (23.2 g). The GC purity was96%.

¹H-NMR(300.4 MHz,solvent:CDCl₃,standard:TMS) δ(ppm):0.87(t,J=6.6Hz,3H),1.18,1.19(d,J=6.3 Hz,d,J=6.3Hz,3H),1.21˜1.32(m,14H),1.47˜1.54(m,2H),3.36˜3.52(m,2H),3.62˜3.72(m,1H),4.22˜4.28,4.33˜4.40(m,2H).

¹⁹F-NMR(282.7 MHz,solvent CDCl₃,standard:CFCl₃)δ(ppm):−80.0(1F),−81.3(3F),−82.1(3F),−86.4(1F),−129.5(2F),−131.5(1F).

Example 23 Production of CF₃(CF₂)₉OCF(CF₃)CF₂OCOCF(CF₃)OCF₂CF₂CF₃

Into a 500 ml autoclave made of nickel, R-113 (312 g) was added, stirredand maintained at 25° C. At the gas outlet of the autoclave, a condensermaintained at 20° C, a NaF pellet packed layer and a condensermaintained at −10° C. were installed in series. Further, a liquidreturning line was installed to return the condensed liquid from thecondenser maintained at −10° C. to the autoclave. Nitrogen gas was blownthereinto for 1 hour, and then fluorine gas diluted to 20% with nitrogengas, was blown thereinto for 1 hour at a flow rate of 10.33 l/hr.

Then, while blowing the fluorine gas at the same flow rate, a solutionhaving CH₃(CH₂)₉OCH(CH₃)CH₂OCOCF(CF₃)OCF₂CF₂CF₃ (4.81 g) obtained inExample 22 dissolved in R-113 (100 g), was injected over a period of 8.0hours. Then, while blowing the fluorine gas at the same flow rate, aR-113 solution having a benzene concentration of 0.01 g/ml was injectedin an amount of 6 ml while raising the temperature from 25° C. to 40° C.and while raising the internal pressure of the autoclave to 0.15 MPa,whereupon the benzene injection inlet of the autoclave was closed, andstirring was continued for 0.3 hour. Then, while maintaining theinternal pressure of the reactor at 0.15 MPa and the internaltemperature of the reactor at 40° C., 3 ml of the above-mentionedbenzene solution was injected, whereupon the benzene injection inlet ofthe autoclave was closed, and stirring was continued for 0.3 hour.Further, the same operation was repeated three times. The total amountof benzene injected was 0.183 g, the total amount of R-113 injected was18 ml.

Further, while blowing the fluorine gas at the same flow rate, stirringwas continued for 0.8 hour. Then, the internal pressure of the reactorwas adjusted to atmospheric pressure, and nitrogen gas was blownthereinto for 1.5 hours. The desired product was quantitatively analyzedby ¹⁹F-NMR, whereby the yield of the above-identified compound was 69%.

¹⁹F-NMR(376.0 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):−80.2˜−81.6(4F),−81.8(2F),−82.3(6F),−82.6(3F),−86.5˜−88.6(3F),−122.5(8F),−122.8(2F),−123.0(2F),−125.8(2F),−126.9(2F),−130.5(2F),−132.4(1F),−145.7and −146.0(1F).

Example 24 Production of CF₃(CF₂)₉OCF(CF₃)COF

CF₃(CF₂)₉OCF(CF₃)CF₂OCOCF(CF₃)OCF₂CF₂CF₃ (2.0 g) obtained in Example 23was charged into a flask together with a NaF powder (0.05 g) and heatedat 150° C. for 24 hours in an oil bath with vigorous stirring. At anupper part of the flask, a reflux condenser adjusted to a temperature of20° C., was installed. After cooling, the liquid sample (1.9 g) wasrecovered. By GC-MS, it was confirmed that CF₃CF(OCF₂CF₂CF₃)COF and theabove-identified compound were the main products. The yield was 63.8%.

Mass spectrum (CI method): 683 (M+H).

Example 25 Production of Compound (IIIc-50)

A compound (Ia-50) (22.7 g) and triethylamine (36.5 g) were put into aflask and stirred in an ice bath. FCOCF(CF₃)OCF₂CF₂CF₃ (60 g) was addeddropwise over a period of 1 hour while maintaining the internaltemperature at a level of not higher than 10° C. After completion of thedropwise addition, stirring was continued at room temperature for 2hours, and the mixture was added to 100 ml of ice water.

The obtained crude liquid was subjected to liquid separation, and thelower layer was washed twice with 100 ml of water, dried over magnesiumsulfate and then subjected to filtration to obtain a crude liquid. Thecrude liquid was distilled under reduced pressure to obtain a compound(IIIc-50) (23.4 g) as a fraction of from 87.5 to 88.5° C./1.4 kPa. TheGC purity was 99%.

¹H-NMR(300.4 MHz,solvent:CDCl₃,standard:TMS) δ(ppm):1.24,1.25(d,J=6.0Hz,dd,J=1.2,6.0 Hz,3H),1.36,1.41(s,3H),3.39˜3.49(m,1H),4.03˜4.42(m,4H).

¹⁹F-NMR(282.7 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):−80.0(1F),−81.4(3F),−82.0˜−82.1(3F),−85.8˜−86.6(1F),−129.5(2F),−131.4˜−131.7(1F) .

Example 26 Production of Compound (IVd-50)

Into a 500 ml autoclave made of nickel, R-113 (313 g) was added, stirredand maintained at 25° C. At the gas outlet of the autoclave, a condensermaintained at 20° C., a NaF pellet packed layer and a condensermaintained at −10° C. were installed in series. Further, a liquidreturning line was installed to return the condensed liquid from thecondenser maintained at −10° C. to the autoclave.

Nitrogen gas was blown thereinto for 1.3 hours, and then fluorine gasdiluted to 20% with nitrogen gas, was blown thereinto for 1 hour at aflow rate of 7.87 l/hr. Then, while blowing the fluorine gas at the sameflow rate, a solution having the compound (IIIc-50) (4.96 g) obtained inExample 25 dissolved in R-113 (100 g), was injected over a period of 5.3hours.

Then, while blowing the fluorine gas at the same flow rate, a R-113solution having a benzene concentration of 0.01 g/ml, was injected in anamount of 9 ml while raising the temperature from 25° C. to 40° C.,whereupon the benzene injection inlet of the autoclave was closed, andthe outlet valve of the autoclave was closed. When the pressure became0.20 MPa, the fluorine gas inlet valve of the autoclave was closed, andstirring was continued for 0.6 hour.

Then, the pressure was adjusted to atmospheric pressure, and whilemaintaining the internal temperature of the reactor at 40° C., 6 ml ofthe above-mentioned benzene solution was injected, whereupon the benzeneinjection inlet of the autoclave was closed, and further, the outletvalve of the autoclave was closed. When the pressure became 0.20 MPa,the fluorine gas inlet valve of the autoclave was closed, and stirringwas continued for 0.6 hour. Further, the same operation was repeatedthree times. The total amount of benzene injected was 0.347 g, and thetotal amount of R-113 injected was 33 ml. Further, nitrogen gas wasblown thereinto for 1.5 hours. The desired product was quantitativelyanalyzed by ¹⁹F-NMR, whereby the yield of the above-identified compoundwas 87%.

¹⁹F-NMR(376.0 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):−78.3(1F),−80.0˜−80.9(4F),−81.4(3F),−81.5˜−82.5(1F),−82.4(3F),−82.6(3F),−86.5˜−88.1(3F),−123.7(1F),−130.6(2F),−132.7(1F).

Example 27 Production of Compound (Ve-50)

The compound (IVd-50) (2.1 g) obtained in Example 26 was charged into aflask together with a NaF powder (0.02 g) and heated for 10 hours at120° C. in an oil bath with vigorous stirring. At an upper portion ofthe flask, a reflux condenser adjusted to a temperature of 20° C., wasinstalled. After cooling, a liquid sample (2.0 g) was recovered. ByGC-MS, it was confirmed that CF₃CF(OCF₂CF₂CF₃)COF and theabove-identified compound were the main products. The NMR yield was71.2%.

¹⁹F-NMR(282.7 MHz,solvent:CDCl₃,standard:CFCl₃) δ(ppm):24.3 and23.7(1F),−77.8˜−79.0(1F),−80.0 and −80.2(3F),−81.3(3F),−83.3 and−83.8(1F),−123.9 and −124.9(1F).

Example 28 Production of Compound (IIIc-51)

A compound (Ia-51) (15 g) was put into a flask and stirred whilebubbling nitrogen gas. FCOCF(CF₃)OCF₂CF₂CF₃ (40 g) was added dropwiseover a period of 30 minutes while maintaining the internal temperaturefrom 25 to 30° C. After completion of the dropwise addition, stirringwas continued at room temperature for 3 hours, and 50 ml of a saturatedsodium hydrogencarbonate aqueous solution was added at an internaltemperature of not higher than 15° C.

The obtained crude oil was subjected to liquid separation, and the lowerlayer was washed twice with 50 ml of water, dried over magnesium sulfateand then subjected to filtration to obtain a crude liquid. The crudeliquid was distilled under reduced pressure to obtain a compound(IIIc-51) (11.3 g) as a fraction of from 99 to 100° C./2.7 kPa. The GCpurity was 99%.

¹H-NMR(399.8 MHz,solvent:CDCl₃,standard:TMS)δ(ppm):1.36,1.42(s,6H),3.78,4.10(dt,J=5.2,8.8 Hz,dd,J=6.4,8.8 Hz,2H),4.31˜4.51(m,3H).

¹⁹F-NMR(376.2 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):−80.3(1F),−81.8(3F),−82.6(3F),−87.0(1F),−130.2(2F),−132.2(1F).

Example 29 Production of Compound (IVd-51)

Into a 500 ml autoclave made of nickel, R-113 (312 g) was added, stirredand maintained at 25° C. At the gas outlet of the autoclave, a condensermaintained at 20° C., a NaF pellet packed layer and a condensermaintained at −10° C. were installed in series. Further, a liquidreturning line was installed to return the condensed liquid from thecondenser maintained at −10° C. to the autoclave. Nitrogen gas was blownthereinto for 1.0 hour, fluorine gas diluted to 20% with nitrogen gas,was blown thereinto for 1 hour at a flow rate of 7.71 l/hr. Then, whileblowing the fluorine gas at the same flow rate, a solution having thecompound (IIIc-51) (5.01 g) obtained in Example 28 dissolved in R-113(100 g), was injected over a period of 5.6 hours.

Then, while blowing the fluorine gas at the same flow rate, a R-113solution having a benzene concentration of 0.01 g/ml, was injected in anamount of 9 ml while raising the temperature from 25° C. to 40° C.,whereupon the benzene injection inlet of the autoclave was closed, andfurther the outlet valve of the autoclave was closed. When the pressurebecame 0.20 MPa, the fluorine gas inlet valve of the autoclave wasclosed, and stirring was continued for 0.9 hour.

Then, the pressure was adjusted to atmospheric pressure, and whilemaintaining the internal temperature of the reactor at 40° C., 6 ml ofthe above-mentioned benzene solution was injected, whereupon the benzeneinjection inlet of the autoclave was closed, and further the outletvalve of the autoclave was closed. When the pressure became 0.20 MPa,the fluorine gas inlet valve of the autoclave was closed, an d stirringwas continued for 0.8 hour. Further, the same operation was repeatedthree times. The total amount of benzene injected was 0.340 g, and thetotal amount of R-113 injected was 33 ml. Further, nitrogen gas wasblown thereinto for 1.5 hours. The desired product was quantitativelyanalyzed by ¹⁹F-NMR, whereby the yield of the above-identified compoundwas 78.2%.

¹⁹F-NMR(376.0 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):−77.9(1F),−79.6˜−80.8(1F),−81.1(3F)−81.2(3F),−81.8˜−82.6(7F),−85.9˜−88.0(3F),−122.6(1F),−130.4 (2F),−132.4and −132.5(1F).

Example 30 Production of Compound (Ve-51)

The compound (IVd-51) (1.8 g) obtained in Example 29 was charged into aflask together with a NaF powder (0.02 g), and heated at 120° C. for 12hours in an oil bath with vigorous stirring. At an upper portion of theflask, a reflux condenser adjusted at the temperature of 20° C., wasinstalled. After cooling, a liquid sample (1.6 g) was recovered. ByGC-MS, it was confirmed that CF₃CF(OCF₂CF₂CF₃)COF and theabove-identified compound were the main products. The NMR spectrum ofthe above-identified compound agreed to the literature values(J.Chin.Chem.Soc.,40,563(1993)), and the yield of the above-identifiedcompound was determined by an internal standard method and found to be73.1%.

Example 31 Production of PhCH₂OCH₂CH₂CH₂OCOCF(CF₃)OCF₂CF₂CF₃

PhCH₂OCH₂CH₂CH₂OH (15 g) having a GC purity of 96%, was put into a flaskand stirred while bubbling nitrogen gas. FCOCF(CF₃)OCF₂CF₂CF₃ (31.5 g)was added dropwise over a period of 30 minutes while maintaining theinternal temperature at from 25 to 30° C. After completion of thedropwise addition, stirring was continued at room temperature for 3hours, and 50 ml of a saturated sodium hydrogencarbonate aqueoussolution was added at an internal temperature of not higher than 15° C.

The obtained crude liquid was subjected to liquid separation, and thelower layer was washed twice with 50 ml of water, dried over magnesiumsulfate and then subjected to filtration to obtain a crude liquid. Thecrude liquid was purified by silica gel column chromatography(developing solvent: AK-225) to obtainPhCH₂OCH₂CH₂CH₂OCOCF(CF₃)OCF₂CF₂CF₃ (14.2 g). The GC purity was 98%.

¹H-NMR(300.4 MHz,solvent:CDCl₃,standard:TMS)δ(ppm):1.98˜2.06(m,2H),3.54(t,J=6.0Hz,2H),4.45˜4.58(m,2H),4.49(s,2H),7.25˜7.34(m,5H).

¹⁹F-NMR(282.7 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):−79.9(1F),−81.3(3F),−82.2(3F),−86.5(1F),−129.5(2F),−131.5(1F).

Example 32 Production of Cy^(F)CF₂OCF₂CF₂CF₂OCOCF(CF₃)OCF₂CF₂CF₃

Into a 500 ml autoclave made of nickel, R-113 (313 g) was added, stirredand maintained at 25° C. At the gas outlet of the autoclave, a condensermaintained at 20° C., a NaF pellet packed layer and a condensermaintained at −10° C. were installed in series. Further, a liquidreturning line was installed to return the condensed liquid from thecondenser maintained at −10° C. to the autoclave.

Nitrogen gas was blown thereinto for 1 hour, and then, fluorine gasdiluted to 20% with nitrogen gas, was blown thereinto for 1 hour at aflow rate of 8.08 l/hr. Then, while blowing the fluorine gas at the sameflow rate, a solution having CyCH₂OCH₂CH₂CH₂OCOCF(CF₃)OCF₂CF₂CF₃ (4.82g) obtained in Example 31 dissolved in R-113 (100 g), was injected overa period of 8.4 hours.

Then, while blowing the fluorine gas at the same flow rate and raisingthe internal pressure of the autoclave to 0.15 MPa, a R-113 solutionhaving a benzene concentration of 0.01 g/ml, was injected in an amountof 6 ml while raising the temperature from 25° C. to 40° C., whereuponthe benzene injection inlet of the autoclave was closed, and stirringwas continued for 0.3 hour. Then, while maintaining the internalpressure of the reactor at 0.15 MPa and the internal temperature of thereactor at 40° C., 3 ml of the above-mentioned benzene solution wasinjected, whereupon the benzene injection inlet of the autoclave wasclosed, and stirring was continued for 0.3 hour. Further, the sameoperation was repeated three times.

The total amount of benzene injected, was 0.186 g, and the total amountof R-113 injected, was 18 ml. Further, while blowing the fluorine gas atthe same flow rate, stirring was continued for 0.8 hour. Then, theinternal pressure of the reactor was adjusted to atmospheric pressure,nitrogen gas was blown thereinto for 1.5 hours. The desired product wasquantitatively analyzed by ¹⁹F-NMR, whereby the yield of theabove-identified compound was 26%.

⁹F-NMR(376.0 MHz,solvent: CDCl₃,standard:CFCl₃)δ(ppm):−79.9˜−84.3(11F),−87.0˜−87.8(3F),−119.5˜−143.5(10F),−129.8(2F),−130.5(2F),−132.5(1F),−187.9(1F)

Example 33 Production of Cy^(F)CF₂OCF₂CF₂COF

Cy^(F)CF₂OCF₂CF₂CF₂OCOCF(CF₃)OCF₂CF₂CF₃ (0.5 g) obtained in Example 32was charged into a flask together with a NaF powder (0.01 g) and heatedat 140° C. for 10 hours in an oil bath with vigorous stirring. At anupper portion of the flask, a reflux condenser adjusted to a temperatureof 20° C., was installed. After cooling, a liquid sample (0.4 g) wasrecovered. From GC-MS, it was confirmed that CF₃CF(OCF₂CF₂CF₃)COF (MS(CImethod): 495 (M+H)) and the above-identified compound were the mainproducts.

Example 34 Production of CH₃CH(OCH₂Ph)CH₂OCOCF(CF₃)OCF₂CF₂CF₃

CH₃CH(OCH₂Ph)CH₂OH (13.1 g) having a GC purity of 96% was put into aflask and stirred while bubbling nitrogen gas. FCOCF(CF₃)OCF₂CF₂CF₃(39.5 g) was added dropwise over a period of 1 hour while maintainingthe internal temperature from 25 to 30° C. After completion of thedropwise addition, stirring was continued at room temperature for 3hours, and 50 ml of a saturated sodium hydrogencarbonate aqueoussolution was added at an internal temperature of not higher than 15° C.

The obtained crude liquid was subjected to liquid separation, and thelower layer was washed twice with 50 ml of water, dried over magnesiumsulfate and the subjected to filtration to obtain a crude liquid.

The crude liquid was purified by silica gel column chromatography(developing solvent: AK-225) to obtainCH₃CH(OCH₂Ph)CH₂OCOCF(CF₃)OCF₂CF₂CF₃ (11 g). The GC purity was 98%.

¹H-NMR(300.4 MHz,solvent:CDCl₃,standard:TMS) δ(ppm):1.23(d,J=6.6Hz,3H),3.76˜3.87(m,1H),4.26˜4.60(m,2H),4.54, 4.56(s,2H),7.26˜7.36(m,5H).

¹⁹F-NMR(282.7 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):−80.0(1F),−81.3(3F),−82.1(3F),−86.4(1F),−129.5(2F),−131.5(1F).

Example 35 Production of Cy^(F)CF₂OCF(CF₃)CF₂OCOCF(CF₃)OCF₂CF₂CF₃

Into a 500 ml autoclave made of nickel, R-113 (312 g) was added, stirredand maintained at 25° C. At the gas outlet of the autoclave, a condensermaintained at 20° C., a NaF pellet packed layer and a condensermaintained at −10° C. were installed in series. Further, a liquidreturning line was installed to return the condensed liquid from thecondenser maintained at −10° C. to the autoclave.

Nitrogen gas was blown thereinto for 1 hour and then, fluorine gasdiluted to 20% with nitrogen gas, was blown thereinto for 1 hour at aflow rate of 8.32 l/hr.

Then, while blowing the fluorine gas at the same flow rate, a solutionhaving CH₃CH(OCH₂Ph)CH₂OCOCF(CF₃)OCF₂CF₂CF₃ (4.97 g) obtained in Example34 dissolved in R-113 (100 g), was injected over a period of 8.0 hours.

Then, while blowing the fluorine gas at the same flow rate and raisingthe internal pressure of the autoclave to 0.15 MPa, a R-113 solutionhaving a benzene concentration of 0.01 g/ml, was injected in an amountof 6 ml while raising the temperature from 25° C. to 40° C., whereuponthe benzene injection inlet of the autoclave was closed, and stirringwas continued for 0.3 hour. Then, while maintaining the internalpressure of the reactor at 0.15 MPa and the internal temperature of thereactor at 40° C., 3 ml of the above-mentioned benzene solution wasinjected, whereupon the benzene injection inlet of the autoclave wasclosed, stirring was continued for 0.3 hour. Further, the same operationwas repeated three times.

The total amount of benzene injected was 0.182 g, and the total amountof R-113 injected was 18 ml. Further, while blowing the fluorine gas atthe same flow rate, stirring was continued for 0.8 hour. Then, theinternal pressure of the reactor was adjusted to atmospheric pressure,and nitrogen gas was blown thereinto for 1.5 hours. The desired productwas quantitatively analyzed by ¹⁹F-NMR, whereby the yield of theabove-identified compound was 22%.

Example 36 Production of CH₃CH(OCH₂CH₂CH═CH₂)COOCH₂CH₂CH═CH₂

CH₃CHClCOOH (50 g) and CH₂═CHCH₂CH₂OH (75 ml) were put into a flask, and10 ml of concentrated sulfuric acid was added dropwise, followed bystirring at room temperature for 10 minutes. The reaction solution waspoured into 250 ml of a saturated sodium carbonate aqueous solution. 150ml of water and 150 ml of t-butylmethyl ether were added for liquidseparation to obtain a t-butylmethyl ether layer as an organic layer.The organic layer was washed with 150 ml of water, dried over magnesiumsulfate and then subjected to filtration to obtain a crude liquid. Thecrude liquid was concentrated to obtain CH₃CHClCOOCH₂CH₂CH═CH₂.

CH₂═CHCH₂CH₂OH (16.6 g) and dimethylformamide (120 ml) were put into aflask and cooled so that the internal temperature was maintained at from8 to 9° C. Sodium hydride (10 g) was added over a period of 30 minutes,and stirring was continued at room temperature of 30 minutes, followedby cooling again. Then, CH₃CHClCOOCH₂CH₂CH═CH₂ (50 g) was dissolved in30 ml of dimethylformamide, which was added dropwise over a period of1.5 hours. After the dropwise addition, heating was continued for 3hours while maintaining the internal temperature at from 80 to 85° C.The temperature was returned to room temperature (25° C.), and 200 ml of2 mol/l hydrochloric acid was added. The mixture was extracted fourtimes with 400 ml of a solution of hexane/ethyl acetate=2/1 to obtain anorganic layer. The organic layer was concentrated and then washed twicewith 500 ml of water, dried over magnesium sulfate and then subjected tofiltration and concentrated again to obtainCH₃CH(OCH₂CH₂CH═CH₂)COOCH₂CH₂CH═CH₂ (36 g) The GC purity was 83%.

¹H-NMR(399.8 MHz,solvent:CDCl₃,standard:TMS) δ(ppm):1.39(d,J=7.0Hz,3H),2.33-2.45(m,4H),3.41(dt,J=7.0, 9.1 Hz,1H),3.63(dt,J=7.0, 9.1Hz,1H),3.96(q,J=7.0Hz,1H),4.15-4.27(m,2H),5.02-5.14(m,4H),5.73-5.88(m,2H).

Example 37 Production of CH₃CH(OCH₂CH₂CH═CH₂)CH₂OH

In an argon atmosphere, lithium aluminum hydride (6.9 g) and 240 ml ofdehydrated diethyl ether were put into a flask and stirred in an icebath. CH₃CH(OCH₂CH₂CH═CH₂)COOCH₂CH₂CH═CH₂ (36 g) having a GC purity of83% obtained in Example 36, was added dropwise thereto over a period of45 minutes and then stirred at room temperature (25° C.) for 3.5 hours.While cooling in an ice bath,100 ml of ice water was added dropwise, and100 ml of water was further added to bring the temperature to roomtemperature (25° C.), followed by filtration. Washing was carried outwith 450 ml of diethyl ether, and the filtrate was subjected to liquidseparation. The aqueous layer was further extracted twice with 200 ml ofdiethyl ether, and the collected diethyl ether layers were obtained asan organic layer. The organic layer was dried over magnesium sulfate andthe subjected to filtration to obtain a crude liquid. The crude liquidwas concentrated to 35 g and distilled under reduced pressure to removea fraction (6.6 g) of from 28 to 49° C./9.33 kPa, and from the residue,CH₃CH(OCH₂CH₂CH═CH₂)CH₂OH (19.2 g) was obtained. The GC purity was 98%.

¹H-NMR(399.8 MHz,solvent:CDCl₃,standard:TMS) δ(ppm):1.12(d,J=6.2Hz,3H),2.35(tq,J=1.3, 6.7Hz,2H),3.42-3.48(m,2H),3.51-3.59(m,2H),3.64-3.69(m,1H),5.04-5.15(m,2H),5.79-5.89(m,1H).

Example 38 Production of CH₃CH(OCH₂CH₂CHClCH₂Cl)CH₂OH

CH₃CH(OCH₂CH₂CH═CH₂)CH₂OH (19.2 g) having a GC purity of 98% obtained inExample 37, was put into a flask and stirred while bubbling nitrogengas. Calcium chloride (2.2 g) and water (3.6 g) were added thereto,followed by cooling to 10° C. Chlorine gas was blown thereinto for 2hours at a supply rate of about 4 g/hr. Then, disappearance of thestarting material was confirmed by GC, and diethyl ether (200 ml) andwater (200 ml) were added. Liquid separation was carried out, and theorganic layer was dried over magnesium sulfate. Then, the solvent wasdistilled off, and the crude product was used as it was in the step ofExample 39.

Example 39 Production of CH₃CH(OCH₂CH₂CHClCH₂Cl)CH₂OCOCF(CF₃)OCF₂CF₂CF₃

The crude product of CH₃CH(OCH₂CH₂CHClCH₂Cl)CH₂OH obtained in Example 38was put into a flask and stirred while bubbling nitrogen gas.FCOCF(CF₃)OCF₂CF₂CF₃ (50 g) was added dropwise over a period of 1 hourwhile maintaining the internal temperature from 25 to 30° C. Aftercompletion of the dropwise addition, stirring was continued at roomtemperature for 3 hours, and 80 ml of a saturated sodiumhydrogencarbonate aqueous solution was added at an internal temperatureof not higher than 15° C.

50 ml of water and 100 ml of chloroform were added, followed by liquidseparation to obtain a chloroform layer as an organic layer. Further,the organic layer was washed twice with 100 ml of water, dried overmagnesium sulfate and then subjected to filtration to obtain a crudeliquid. The crude liquid was concentrated and then purified by silicagel column chromatography (developing solvent: hexane:ethylacetate=40:1), and then purified again by silica column chromatography(developing solvent: AK-225) to obtain 37 g ofCH₃CH(OCH₂CH₂CHClCH₂Cl)CH₂OCOCF(CF₃)OCF₂CF₂CF₃. The GC purity was 88%.

¹H-NMR(399.8 MHz,solvent:CDCl₃,standard:TMS) δ(ppm):1.21(dd,J=1.3,6.3Hz,3H),1.81-1.93(m,1H),2.19-2.26(m,1H),3.59-3.65(m,1H),3.68-3.80(m,4H),4.20-4.46(m,3H).

¹⁹F-NMR(376.2 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):−80.3(1F),−81.6(3F),−82.4(3F),−86.7(1F),−130.0(2F),−132.0(1F).

Example 40 Production of CF₂ClCFClCF₂CF₂OCF(CF₃)CF₂OCOCF(CF₃)OCF₂CF₂CF₃

Into a 500 ml autoclave made of nickel, R-113 (313 g) was added, stirredand maintained at 25° C. At the gas outlet of the autoclave, a condensermaintained at 20° C., a NaF pellet packed layer and a condensermaintained at −10° C. were installed in series. Further, a liquidreturning line was installed to return the condensed liquid from thecondenser maintained at −10° C. to the autoclave.

Nitrogen gas was blown thereinto for 1.3 hours, and then fluorine gasdiluted to 20% with nitrogen gas, was blown thereinto for 1 hour at aflow rate of 5.77 l/hr. Then, while blowing the fluorine gas at the sameflow rate, a solution havingCH₂ClCHClCH₂CH₂OCH(CH₃)CH₂OCOCF(CF₃)OCF₂CF₂CF₃ (4.63 g) obtained inExample 39 dissolved in R-113 (100 g), was injected over a period of 7.3hours.

Then, while blowing the fluorine gas at the same flow rate, a R-113solution having a benzene concentration of 0.01 g/ml, was injected in anamount of 6 ml while raising the temperature from 25° C. to 40° C.,whereupon the benzene injection inlet of the autoclave was closed, andfurther, the outlet valve of the autoclave was closed. When the pressurebecame 0.20 MPa, the fluorine gas inlet valve of the autoclave wasclosed, and stirring was continued for 1 hour. Then, the pressure wasreturned to atmospheric pressure, and while maintaining the internaltemperature of the reactor at 40° C.,3 ml of the above-mentioned benzenesolution was injected, whereupon the benzene injection inlet of theautoclave was closed, and further, the outlet valve of the autoclave wasclosed. When the pressure became 0.20 MPa, the fluorine gas inlet valveof the autoclave was closed, and stirring was continued for 1 hour.

Further, the same operation was repeated seven times. The total amountof benzene injected was 0.288 g, and the total amount of R-113 injectedwas 29 ml. Further, nitrogen gas was blown thereinto for 1.5 hours. Thedesired product was quantitatively analyzed by ¹⁹F-NMR, whereby theyield of the above-identified compound was 63%.

¹⁹F-NMR(376.0 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):−64.7(2F),−76.5˜−80.0(1F),−80.0˜−81.0(4F),−82.2(3F),−82.5(3F),−82.0˜−82.9(1F),−86.4˜−88.1(3F),−117.0˜−119.7(2F),−130.4(2F),−131.9(1F),−132.3(1F),−145.9(1F).

Example 41 Production of CH₂═CHCH₂OCH₂CH₂CH₂OCOCF(CF₃)OCF₂CF₂CF₃

CH₂═CHCH₂OCH₂CH₂CH₂OH (13.9 g) having a GC purity of 99% andtriethylamine (25.4 g) were put into a flask and stirred in an ice bath.FCOCF(CF₃)OCF₂CF₂CF₃ (41.7 g) was added dropwise over a period of 2hours while maintaining the internal temperature at a level of nothigher than 10° C. After completion of the dropwise addition, stirringwas continued at room temperature for 1 hour, and the mixture was addedto 50 ml of ice water.

The obtained crude liquid was subjected to liquid separation, and thelower layer was washed twice with 50 ml of water, dried over magnesiumsulfate and then subjected to filtration, to obtain a crude liquid. Bydistillation under reduced pressure,CH₂═CHCH₂OCH₂CH₂CH₂OCOCF(CF₃)OCF₂CF₂CF₃ (30.3 g) was obtained as afraction of from 89 to 90° C./1.2 kPa. The GC purity was 99%.

¹H-NMR(300.4 MHz,solvent:CDCl₃,standard:TMS)δ(ppm):1.95˜2.03(m,2H),3.48(t,J=6.0 Hz,2H),3.94 (dt,J=1.5,6.0Hz,2H),4.42˜4.55(m,2H),5.16(d,J=10.5 Hz,1H),5.24(d,J=17.1Hz,1H),5.80˜5.93(m,1H).

¹⁹F-NMR(282.7 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):−79.9(1F),−81.3(3F),−82.2(3F),−86.6(1F),−129.5(2F),−131.5(1F).

Example 42 CF₃CF₂CF₂OCF₂CF₂CF₂OCOCF(CF₃)OCF₂CF₂CF₃

Into a 500 ml autoclave made of nickel, R-113 (312 g) was added, stirredand maintained at 25° C. At the gas outlet of the autoclave, a condensermaintained at 20° C., a NaF pellet packed layer and a condensermaintained at −10° C. were installed in series. Further, a liquidreturning line was installed to return the condensed liquid from thecondenser maintained at −10° C. to the autoclave. Nitrogen gas was blownthereinto for 1.0 hour, and then fluorine gas diluted to 20% withnitrogen gas, was blown thereinto for 1 hour at a flow rate of 6.47l/hr.

Then, while blowing the fluorine gas at the same flow rate, a solutionhaving CH₂═CHCH₂OCH₂CH₂CH₂OCOCF(CF₃)OCF₂CF₂CF₃ (4.99 g) obtained inExample 41 dissolved in R-113 (100 g), was injected over a period of 8.0hours.

Then, while blowing the fluorine gas at the same flow rate, a R-113solution having a benzene concentration of 0.01 g/ml was injected in anamount of 9 ml while raising the temperature from 25°0 C. to 40° C.,whereupon the benzene injection inlet of the autoclave was closed, andfurther the outlet valve of the autoclave was closed. When the pressurebecame 0.20 MPa, the fluorine gas inlet valve of the autoclave wasclosed, and stirring was continued for 0.6 hour. Then, the pressure wasadjusted to atmospheric pressure, and while maintaining the internaltemperature of the reactor at 40° C.,6 ml of the above-mentioned benzenesolution was injected, whereupon the benzene injection inlet of theautoclave was closed, and further the outlet valve of the autoclave wasclosed. When the pressure became 0.20 MPa, the fluorine gas inlet valveof the autoclave was closed, and stirring was continued for 0.8 hour.Further, the same operation was repeated once.

The total amount of benzene injected, was 0.219 g and the total amountof R-113 injected was 21 ml. Further, nitrogen gas was blown thereintofor 1.5 hours. The desired product was quantitatively analyzed by¹⁹F-NMR, whereby the yield of the above-identified compound was 85.8%.

¹⁹F-NMR(376.0 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):−79.9(1F),−82.1(6F),−82.3(3F),−83.9(2F),−84.7(2F),−86.9(1F),−87.4(2F),−129.6(2F),−130.2(2F),−130.5(2F),−132.2(1F).

Example 43 Production of CF₃CF₂CF₂OCF₂CF₂COF

CF₃CF₂CF₂OCF₂CF₂CF₂OCOCF(CF₃)OCF₂CF₂CF₃ (0.8 g) obtained in Example 42was charged into a flask together with a NaF powder (0.01 g) and heatedat 120° C. for 10 hours in an oil bath with vigorous stirring. At anupper portion of the flask, a reflux condenser adjusted to a temperatureof 20° C. was installed. After cooling, a liquid sample (0.7 g) wasrecovered. By GC-MS, it was confirmed that CF₃CF(OCF₂CF₂CF₃)COF and theabove-identified compound were the main products. The yield was 57.0%.

¹⁹F-NMR(376.0 MHz,solvent:CDCl₃,standard:CFCl₃)δ(ppm):24.4(1F),−81.9(3F),−84.7(2F),−85.9(2F),−121.7(2F),−130.4(2F).

Example 44 Production of CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂CH₂CH₃)CH₃ andCF₃(CF₃CF₂CF₂O)CFCOOCH(CH₃)CH₂(OCH₂CH₂CH₃)

In a 500 ml four-necked reactor equipped with a Dinroth condenser anddropping funnel, triethylamine (127 ml) was added to a mixture (77.7 g)of 2-propoxy-1-propanol,1-propoxy-2-propanol and 1-propanol in a ratioof 62:34:4 (molar ratio) obtained by synthesizing from propylene oxideand 1-propanol by a method disclosed in a literature (J.Chem.Soc.PerkinTrans.2,199(1993)), followed by distillation under reduced pressure, andthe mixture was stirred. FCOCF(CF₃)OCF₂CF₂CF₃ (151.4 g) was addeddropwise over a period of 1.5 hours while maintaining the internaltemperature at a level of not higher than −10° C. After completion ofthe dropwise addition, stirring was continued at room temperature for 1hour, and the mixture was added to 400 ml of ice water. AK-225 (400 ml)was added thereto, followed by mixing by shaking, and the mixture wasseparated by a separating funnel. The organic layer was washed with 400ml of water and concentrated by an evaporator. The residue (193.1 g) waspurified by silica gel column chromatography, followed by distillationto obtain a mixture (90.8 g) of CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂CH₂CH₃)CH₃and CF₃(CF₃CF₂CF₂O)CFCOOCH(CH₃)CH₂(OCH₂CH₂CH₃) in a ratio of 66.1:33.9(molar ratio).

Example 45 Production of CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCF₂CF₂CF₃)CF₃ andCF₃(CF₃CF₂CF₂O)CFCOOCF(CF₃)CF₂(OCF₂CF₂CF₃)

Into a 3000 ml autoclave made of nickel, R-113(1873 g) was added,stirred and maintained at 250° C. At the gas outlet of the autoclave, acondenser maintained at 25° C., a NaF pellet packed layer and acondenser maintained at −10° C. were installed in series. Further, aliquid returning line was installed to return the condensed liquid fromthe condenser maintained at −10° C. to the autoclave. Nitrogen gas wasblown thereinto for 1.5 hours, and then fluorine gas diluted to 20% withnitrogen gas, was blown thereinto for 3 hours at a flow rate of 8.91l/hr.

Then, while blowing the fluorine gas at the same flow rate, a solutionhaving the mixture (39.95 g) of CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂CH₂CH₃)CH₃and CF₃(CF₃CF₂CF₂O)CFCOOCH(CH₃)CH₂(OCH₂CH₂CH₃) obtained in theproduction of Example 44 dissolved in R-113 (798.8 g), was injected overa period of 42.5 hours.

Then, while blowing the fluorine gas at the same flow rate, a R-113solution having a benzene concentration of 0.01 g/ml, was injected in anamount of 18 ml while raising the temperature from 25° C. to 40° C.,whereupon the benzene injection inlet of the autoclave was closed, andfurther the outlet valve of the autoclave was closed. When the pressurebecame 0.20 MPa, the fluorine gas inlet valve of the autoclave wasclosed, and stirring was continued for 1 hour. Then, the pressure wasadjusted to atmospheric pressure, and while maintaining the internaltemperature of the reactor at 40° C.,6 ml of the above-mentioned benzenesolution was injected, whereupon the benzene injection inlet of theautoclave was closed, and further the outlet valve of the autoclave wasclosed. When the pressure became 0.20 MPa, the fluorine gas inlet valveof the autoclave was closed, and stirring was continued for 1 hour.Further, the same operation was repeated once. The total amount ofbenzene injected, was 0.309 g, and the total amount of R-113 injected,was 30 ml. Further, nitrogen gas was blown thereinto for 2.0 hours. Thedesired product was quantitatively analyzed by ¹⁹F-NMR, whereby theyields of the above-identified compounds were 93% and 91%, respectively.

Example 46 Production of CF₃CF(OCF₂CF₂CF₃)COF

CF₃CF(OCF₂CF₂CF₃)COOCF₂(OCF₂CF₂CF₃)CF₃(6.6 g) obtained in Example 2 wascharged into a flask together with a NaF powder (0.13 g) and heated at120° C. for 4.5 hours and at 140° C. for 2 hours in an oil bath withvigorous stirring. Through a reflux condenser adjusted at a temperatureof 70° C., installed at an upper portion of the flask, a liquid sample(5.0 g) was recovered. By GC-MS, it was confirmed thatCF₃CF(OCF₂CF₂CF₃)COF was the main product. The NMR yield was 72.6%.

Example 47 Production of CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCF₂CF₂CF₃)CF₃

Into a 3000 ml autoclave made of nickel, R-113 (1890 g) was added,stirred and maintained at 25° C. At the gas outlet of the autoclave, acondenser maintained at 20° C., a NaF pellet packed layer and acondenser maintained at −10° C. were installed in series. Further, aliquid returning line was installed to return the condensed liquid fromthe condenser maintained at −10° C. to the autoclave. Nitrogen gas wasblown thereinto for 1.5 hours, and then, fluorine gas diluted to 20%with nitrogen gas, was blown thereinto for 3 hours at a flow rate of8.91 l/hr.

Then, while blowing the fluorine gas at the same flow rate, a solutionhaving dissolved in R-113 (601 g)CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂CH₂CH₃)CH₃ (60.01 g) synthesized fromCF₃(CF₃CF₂CF₂O)CFCOF and 2-propoxy-1-propanol obtained by synthesizingfrom propylene oxide and 1-propanol by a method disclosed in aliterature (J.Chem.Soc.Perkin Trans. 2,199(1993)), followed bypurification, was injected over a period of 63.7 hours.

Then, while blowing the fluorine gas at the same flow rate, a R-113solution having a benzene concentration of 0.01 g/ml, was injected in anamount of 18 ml while raising the temperature from 25° C. to 40° C.,whereupon the benzene injection inlet of the autoclave was closed, andfurther the outlet valve of the autoclave was closed. When the pressurebecame 0.20 MPa, the fluorine gas inlet valve of the autoclave wasclosed, and stirring was continued for 1 hour. Then, the pressure wasadjusted to atmospheric pressure, and while maintaining the internaltemperature of the reactor at 40° C.,6 ml of the above-mentioned benzenesolution was injected, whereupon the benzene injection inlet of theautoclave was closed, and further the outlet valve of the autoclave wasclosed. When the pressure became 0.20 MPa, the fluorine gas inlet valveof the autoclave was closed, and stirring was continued for 1 hour.Further, the same operation was repeated once.

The total amount of benzene injected, was 0.309 g, and the total amountof R-113 injected, was 30 ml. Further, nitrogen gas was blown thereintofor 2.0 hours. After the reaction, distillation purification was carriedout to obtain the above-identified compound (86 g).

Example 48 Production of CF₃CF(OCF₂CF₂CF₃)COF

CF₃CF(OCF₂CF₂CF₃)COOCF₂(OCF₂CF₂CF₃)CF₃ (55.3 g) obtained in Example 47was charged into a flask together with a NaF powder (0.7 g) and heatedat 140° C. for 15 hours in an oil bath with vigorous stirring. Through areflux condenser adjusted at a temperature of 70° C., installed at anupper portion of the flask, a liquid sample (52.1 g) was recovered.Distillation purification was carried out, and by GC-MS, it wasconfirmed that CF₃CF(OCF₂CF₂CF₃)COF was the main product. The yield wasobtained and found to be 90.4%.

Example 49 Continuous Production Process

Using CF₃CF(OCF₂CF₂CF₃)COF (46.5 g) obtained in Example 48 and2-propoxy-1-propanol (16.5 g), the reaction was carried out in the samemanner as in Example 1 to obtainCF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂CH₂CH₃)CH₃ (48.0 g).

INDUSTRIAL APPLICABILITY

According to the present invention, it is possible to produce a compound(Ve) which used to be difficult to synthesize or a compound (Ve) whichused to be synthesized by an economically disadvantageous method in ashort process and in good yield from a compound (Ia). The compound (Ia)is usually readily available and can easily be synthesized and isinexpensive, and compounds of various structures are available. Further,by selecting the structures of R^(A) and R^(B) in the compound (Ve), itwill be readily soluble in solvent-2 at the time of fluorination, andthe fluorination reaction can be proceeded in a liquid phase, wherebythe fluorination reaction can be carried out in good yield.

Further, by selecting the structures of R^(A) and R^(B), separation ofthe product (Ve) will be unnecessary. Further, the formed compound (Ve)can be recycled as a compound (IIb) again for the reaction with thecompound (Ia), whereby the compound (Ve) can be produced by a continuousprocess. Further, according to the present invention, a novel compounduseful as a fluorine resin material will be provided.

What is claimed is:
 1. A process for producing a fluorine-containingcompound, which comprises: reacting compound (I) with compound (II) toform compound (III) having a fluorine content ranging from 30-76% by wt;fluorinating compound (III) in a liquid phase to form compound (IV); andconverting compound (IV) to compound (V), compound (VI) or a combinationof compounds (V) and (VI): R^(A)—E¹ (I) R^(B)—E² (II) R^(A)—E-R^(B)(III) R^(AF)—E^(F)-R^(BF) (IV) R^(AF)—E^(F1) (V) R^(BF)—E^(F2) (VI) wherein R^(A), R^(B): each independently is a monovalent saturatedhydrocarbon group, a halogeno monovalent saturated hydrocarbon group, ahetero atom-containing monovalent saturated hydrocarbon group, ahalogeno (hetero atom-containing monovalent saturated hydrocarbon)group, or a monovalent organic group (R^(H)) which can be converted toR^(HF) by a fluorination reaction in a liquid phase, R^(HF): a grouphaving at least one hydrogen atom in a group selected from the groupconsisting of a monovalent saturated hydrocarbon group, a partiallyhalogeno monovalent saturated hydrocarbon group, a heteroatom-containing monovalent saturated hydrocarbon group, and a partiallyhalogeno (hetero atom-containing monovalent saturated hydrocarbon)group, substituted by a fluorine atom; R^(AF), R^(BF): R^(AF) is a groupcorresponding to R^(A), and R^(BF) is a group corresponding to R^(B);and in the instance where each of R^(A) and R^(B) is a monovalentsaturated hydrocarbon group, a halogeno monovalent saturated hydrocarbongroup, a hetero atom-containing monovalent saturated hydrocarbon group,or a halogeno (hetero atom-containing monovalent saturated hydrocarbon)group, R^(AF) and R^(BF) are the same groups as R^(A) and R^(B),respectively, or are R^(A) and R^(B) groups each substituted by at leastone fluorine atom, and in the case where R^(A) and R^(B) are monovalentorganic groups (R^(H)), R^(AF) and R^(BF) are R^(HF), respectively; E¹,E²: reactive groups which are mutually reactive to form a bivalentconnecting group (E); E: a bivalent connecting group formed by thereaction of E¹ and E²; E^(F): the same group as E, or a group in which Eis fluorinated, provided that at least one of R^(AF), R^(BF) and E^(F),is not the same group as the corresponding R^(A), R^(B) and E,respectively; E^(F1), E^(F2): each independently is a group formed bydissociation of E^(F).
 2. The process according to claim 1, wherein thefluorine content of compound (I) is less than 10 wt %.
 3. The processaccording to claim 1, wherein the molecular weight of the compound (III)is from 200 to 1,000.
 4. The process according to claim 1, wherein R^(B)is R^(BF).
 5. The process according to claim 1, wherein each of R^(AF)and R^(BF) is a perfluoro monovalent saturated hydrocarbon group, aperfluoro(partially halogeno monovalent saturated hydrocarbon) group, aperfluoro(hetero atom-containing monovalent saturated hydrocarbon)group, or a perfluoro[partially halogeno(hetero atom-containingmonovalent saturated hydrocarbon)] group.
 6. The process according toclaim 1, wherein the compound (V) has the same structure as the compound(VI).
 7. The process according to claim 1, wherein the compound (II) hasthe same structure as the compound (VI).
 8. The process according toclaim 1, wherein the compound (V) has the same structure as the compound(VI) and the same structure also as the compound (II).
 9. The processaccording to claim 7, wherein a part or whole of the compound (VI)formed by the conversion of the compound (IV) is used again for thereaction with the compound (I).
 10. The process according to claim 1,wherein the compound (I) is the following compound (Ia), the compound(II) is the following compound (IIb), the compound (III) is thefollowing compound (IIIc), the compound (IV) is the following compound(IVd), the compound (V) is the following compound (Ve), and the compound(VI) is the following compound (VIf), provided that R^(A), R^(B), R^(AF)and R^(BF) have the same meanings as the meanings in claim 1, and X is ahalogen atom: R^(A)CH₂OH (Ia) XCOR^(B) (IIb) R^(A)CH₂OCOR^(B) (IIIc)R^(AF)CF₂OCOR^(BF) (IVd) R^(AF)COF (Ve) R^(BF)COF (VIf).
 11. The processaccording to claim 10, wherein X is a fluorine atom.
 12. The processaccording to claim 10, wherein R^(AF) and R^(BF) have the samestructure.
 13. The process according to claim 10, wherein the compound(Ia) is the following compound (Ia-2), the compound (IIb) is thefollowing compound (IIb-2), the compound (IIIc) is the followingcompound (IIIc-2), the compound (IVd) is the following compound (IVd-2),the compound (Ve) is the following compound (Ve-2), and the compound(VIf) is the following compound (IIb-2): R¹CH₂OH (Ia-2) FCOR² (IIb-2)R¹CH₂OCOR² (IIIc-2) R³CF₂OCOR² (IVd-2) R³COF (Ve-2) wherein R¹: an alkylgroup, an alkoxyalkyl group, a halogenoalkyl group, or ahalogeno(alkoxyalkyl) group; R²: a perhalogenoalkyl group, or aperhalogeno(alkoxyalkyl) group; R³: a group corresponding to R¹; andwhen R¹ is a group containing no hydrogen atom, it is the same group asR¹, and when R¹ is a group containing hydrogen atoms, it is a grouphaving all of the hydrogen atoms in said group substituted by fluorineatoms.
 14. The process according to claim 13, wherein R² and R³ have thesame structure.
 15. The process according to claim 13, wherein a part orwhole of the compound (IIb-2) formed by the conversion of the compound(IVd-2) is used again for the reaction with the compound (Ia-2).
 16. Theprocess according to claim 10, wherein the conversion reaction of thecompound (IV) is a decomposition reaction by heat, or a dissociationreaction carried out in a liquid phase in the presence of a nucleophileor an electrophile.
 17. The process according to claim 16, wherein thenucleophilic agent is a fluoride anion.
 18. The process according toclaim 1, wherein the fluorination in the liquid phase is a fluorinationreaction with fluorine gas carried out in a liquid phase, or anelectrochemical fluorination reaction.
 19. The process according toclaim 1, wherein the fluorination in the liquid phase is conducted byemploying one member selected from the group consisting of compound(IV), compound (V) and compound (VI), as the liquid phase.
 20. Acompound of one of the following formulas:CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂CH₂CH₃)CH₃, CF₃CF₂COOCH₂CH₂CHClCH₂Cl,CF₂ClCFClCF₂COOCH₂CH₂CHClCH₂Cl, CF₂ClCF₂CFClCOOCH₂CH₂CHClCH₂Cl,CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂CH₂CHClCH₂Cl)CH₃,CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂Cy)CH₃,CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(OCH₂Ph)CH₃,CF₃(CF₃CF₂CF₂O)CFCOOCH₂CH(O(CH₂)₉CH₃)CH₃,CF₃(CF₃CF₂CF₂O)CFCOO(CH₂)₃OCH₂Ph, CF₃(CF₃CF₂CF₂O)CFCOO(CH₂)₃OCH₂CH═CH₂,

wherein Cy is a cyclohexyl group and Ph is a phenyl group.
 21. Acompound of one of the following formulas:CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCF₂CF₂CF₃)CF₃, CF₃CF₂COOCF₂CF₂CFClCF₂Cl,CF₂ClCFClCF₂COOCF₂CF₂CFClCF₂Cl, CF₂ClCF₂CFClCOOCF₂CF₂CFClCF₂Cl,CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(OCF₂CF₂CFClCF₂Cl)CF₃,CF₃(CF₃CF₂CF₂O)CFCOOCF2CF(OCF₂Cy^(F))CF₃,CF₃(CF₃CF₂CF₂O)CFCOOCF₂CF(O(CF₂)₉CF₃)CF₃,CF₃(CF₃CF₂CF₂O)CFCOO(CF₂)₃OCF₂Cy^(F),CF₃(CF₃CF₂CF₂O)CFCOO(CF₂)₃OCF₂CF₂CF₃,

wherein Cy^(F) is a perfluorocyclohexyl group.
 22. A compound of one ofthe following formulas: FCOCF(O(CF₂)₉CF₃)CF₃ FCO(CF₂)₂OCF₂CY^(F).
 23. Aprocess for producing a fluorine-containing compound, which comprises:reacting compound (I) of the formula R^(A)—E¹ having a fluorine contentof less than 10 wt %, wherein R^(A) is a monovalent C₁₋₂₀ saturatedhydrocarbon group, a halogeno monovalent C₁₋₂₀ saturated hydrocarbongroup, a oxygen atom-containing monovalent C₁₋₈ saturated hydrocarbongroup bonded to a C₁₋₂₀ saturated hydrocarbon group , a halogeno (oxygenatom-containing monovalent saturated hydrocarbon) group, or a monovalentorganic group (R^(H)) which can be converted to R^(HF) by thesubstitution of fluorine for at least one hydrogen atom in R^(A) and E¹is —CH₂OH, with compound (II) having the formula R^(B)—E², wherein R^(B)independently is as defined for R^(A) and E² is —COX or —SO₂X, therebyforming compound (III) having the formula R^(A)—E—R^(B) which has afluorine content ranging from 30-76% by wt, wherein R^(A) and R^(B) areas defined above and E is —COOCH₂— or —SO₂OCH₂—; fluorinating compound(III) in a liquid phase to form compound (IV) of the formulaR^(AF)—E^(F)-R^(BF), wherein R^(AF) and R^(BF) represent R^(A) and R^(B)respectively which are substituted by fluorine in the fluorinationreaction and E^(F) is the same as E as defined above or fluorinated E,provided that at least one of R^(AF), R^(BF) and E^(F) is not the samegroup as the corresponding R^(A), R^(B) and E respectively; andconverting compound (IV) to compound (V) having the formulaR^(AF)—E^(F1), wherein R^(AF) is as defined above and E^(F1) is formedby the dissociation of E^(F), or to a compound (VI) having the formulaR^(BF)—E^(F2), wherein R^(BF) is as defined above and E^(F2) is formedby the dissociation of E^(F), or to both compound (V) and compound (VI).24. A process for producing a fluorine-containing compound, whichcomprises: reacting a compound (I) of a formula selected from the groupconsisting of CH₃(CH₃CH₂CH₂O)CHCH₂OH, CH₃(CH₂ClCHClCH₂CH₂O)CHCH₂OH,CH₃(BrCH₂CH₂O)CHCH₂OH, CH₃[CH₂ClCHClCH₂CH(CH₃)O]CHCH₂OH, CH₃CH₂CH₂OH,CH₂═CHCH₂OH, CH₂ClCHClCH₂CH₂OH, CH₂ClCH₂OH, CH₂BrCH₂OHCyCH₂OCH(CH₃)CH₂OH, PhCH₂OCH(CH₃)CH₂OH, CH₃(CH₂)₉OCH(CH₃)CH₂OHPhCH₂O(CH₂)₂CH₂OH, CH₂═CHCH₂O(CH₂)₂CH₂OH, CH₃CH₂CH₂OCH₂CH(CH₃)OH,CF₂ClCFClCH₂CH₂OH,

wherein Cy is cyclohexyl and Ph is phenyl, with a compound (II) of aformula selected from the group consisting of CF₂CF₂COF,CF₂ClCFClCF₂COF, CF₂ClCF₂CFClCOF, CF₃(CF₃CF₂CF₂O)CFCOF;CF₃(CF₂ClCFClCF₂CF₂O)CFCOF, CClF₂COF, CF₃(CF₂BrCF₂O)CFCOF,CF₃[CF₂ClCFClCF₂CF(CF₃)O]CFCOF, CF₃CF₂CF₂OCF(CF₃)CF₂OCF(CF₃)COF,CF₃(CH₃CH₂CH₂O)CFCOF, CH₂ClCHClCH₂COCl, thereby forming an esterintermediate (III); fluorinating ester intermediate (III) in a liquidphase to form a more extensively fluorinated compound (IV); anddecomposing compound (IV) thermally or in the presence of anelectrophile or a nucleophile, thereby forming a fluorinated compound(V) or fluorinated compound (VI) or both.